CHEMISTRY

Code No. 1/2

Time Allowed: 3 Hours

Set: 1
Maximum Marks: 100

Section A
Answer1: Since formation of carbocation is the rate-determining step in the S N 1 reaction, the
stability of carbocation would determine its reactivity.
The order of stability of carbocation is as follows:
Tertiary > Secondary > Primary >Methyl
Here, 1-chloro-1-methylpropane would form secondarycarbocation, while 1chloro-2-methylpropane will form primary carbocation, which is less stable than
secondary carbocation. Hence, reactivity towards the SN1 reaction would be higher
for 1-chloro-1-methylpropane.
Answer2: On adding NaOH to ammonium sulphate, ammonia gas is evolved. It has a pungent
odour and forms a blue-coloured complex with the Cu2+ ion.
The concerned chemical reactions are as follows:

Answer3: Ferromagnetism is shown by the substances for which the magnetic moments of
domains are arranged in the same direction.
Answer4: The IUPAC name of the given compound is 2, 4, 6-tribromoaniline.

Answer5: There are two main reasons for the stability of colloidal sols:
1. Electrostatic stabilisation: Presence of equal and similar charges on the colloidal
particles prevents coagulation of the colloidal sol.
2. Solvation: Colloidal particles are covered by a sheath of liquid in which they are
extensively solvated, thereby providing stability.
Section B
Answer6: (i) Mercury cell is used in hearing aids.
(ii) Fuel cell was used in the Apollo space programme.
(iii) Lead storage cell is used in automobiles and inverters.
(iv) Dry cell does not have a long life.
Answer7: Chromite ore, on fusion with NaOH, forms sodium chromate (yellow-coloured
compound):

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4 FeCr2O4 + 16 NaOH + 7 O2
8 Na2CrO4 + 2 Fe2O3 + 8 H 2O

( A)

= Na2CrO4

Sodium chromate, on acidification, gives sodium dichromate (B):

2 Na2CrO4 + H 2 SO4 Na2Cr2O7 + Na2 SO4 + H 2O

( B)

= Na2Cr2O7

Sodium dichromate, on reaction with KCl, forms potassium dichromate (orangecolouredcrytalline compound):
Na2Cr2O7 + 2 KCl K 2Cr2O7 + 2 NaCl

(C )

= K 2Cr2O7

One use of potassium dichromate is that it is a powerful oxidising agent. It is used

in preparation of azo compounds. It is also used in leather industry.
Disclaimer: Students can write any one use of potassium dichromate.
OR

2
( i ) 8 MnO4 + 3 S2O3 + H 2O 8 MnO2 + 6 SO42 + 2 OH

( ii ) Cr 2O72 + 3 Sn2+ + +14 H + 2 Cr 3+ + 3 Sn4+ + 7 H 2O

Answer8: As two moles of AgCl are obtained; therefore, the structural formula would contain
two Cl ions satisfying the primary valencies, while five H2O molecules and one Cl
ion are present inside the coordination sphere, making the coordination number 6.
One H2O molecule will be present as the molecule of hydration.
Structural formula: [CrCl(H2O)5]Cl2.H2O : CrCl ( H 2O )5 Cl2 .H 2O
IUPAC name of the compound: Pentaaquachloridochromium(III) chloride
Answer9: (i) This reaction is catalysed by Pt at high pressure. So, it is a zero-order reaction
with molecularity 2.
(ii) The rate law expression for this reaction is
Rate = k
Hence, the unit of k is mol L1 s1.
Answer10: The mechanism of the given reaction is as follows:
(i) Protonation of an alcohol molecule

(ii) Attack of other alcohol molecule on the protonated molecule

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(iii) Deprotonation

Section - C
Answer11: (i) In chlorobenzene, the CCl bond gets partial double bond character because of
the +M effect shown by the Cl group. Due to double bond character, the bond
length decreases in chlorobenzene as compared to the normal CH3Cl bond length.
Therefore, the CCl bond length in chlorobenzene is shorter than the CCl bond
length in CH3Cl.
(ii) Reasons behind the dipole moment of chlorobenzene being lower than that of
cyclohexyl chloride are follows:
(a) In chlorobenzene, the CCl bond is shorter due to partial double bond character.
(b) Hybridisations of C in CCl in chlorobenzene and cyclohexyl chloride are sp2 and
sp3, respectively (sp2 C being more electronegative than sp3 C).
As dipole moment is the product of charge and bond distance, both the factors in
chlorobenzene are lower as compared to cyclohexyl chloride. Therefore, the
dipole moment of chlorobenzene is lower than that of cyclohexyl chloride.
(iii) In SN1 reaction, formation of carbocation as an intermediate takes place. This
carbocation has sp2-hybridised and planar structure. This planar carbocation is
attacked by nucleophile from both the sides equally to form d and l isomers in
equal proportion. Such products are called racemic mixture. Hence, SN1 reactions
are accompanied by racemisation in optically active alkyl halides.
Answer12: Given:
a = 250 pm = 250 1012 m
z=4
m = 300 g
M
(M is molar mass.)
m=
NA
Molar mass, M =
Density, d =

300 6.02 1023

= 90.3 g / mol
2 1024

zM
a3 N A

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d=

4 90.3

( 250 )

10

36

6.02 10

23

= 38.4 g / cm3

Therefore, the density of the given element is 38.4 g/cm3

Answer13: Given:
Order of the reaction = First order
t1/2 = 200 minutes = 200 60 = 12,000 seconds
The relation between t1/2 and k is given by
t1/2 = 0.693/k
k = 0.693/12000 = 5.7 105
The rate constant for the first-order decomposition of H2O2 is given by
1.0 104
log k = 14.2
..... ( i )
T
By Arrhenius equation
Ea
log k = log A
..... ( ii )
2.303RT
Comparing (i) and (ii), we get
Ea = 1.91 105
Answer14: (i) Adsorption is a surface phenomenon that causes the accumulation of
molecules of a substance at the surface of a solid or liquid rather than in the bulk.
In adsorption, the substance gets concentrated at the surface only. It does not
penetrate through the surface to the bulk of the solid or liquid. For example, when
a chalk stick is dipped into an ink solution, only its surface becomes coloured.
On the other hand, the process of absorption is a bulk phenomenon. In absorption,
the absorbed substance gets uniformly distributed throughout the bulk of the solid
or liquid.
(ii) According to the Schulze-Hardy rule, the effectiveness of the salt causing
flocculation depends on the charge on the ion of opposite sign to the charge on
the sol particles. The greater the magnitude of the opposite charge, the higher the
ability of a salt to coagulate the sol.
Thus, trivalent salt AlCl3 is more effective in causing the coagulation of a
negatively charged sol than divalent salt MgCl2 .
(iii) Out of sulphur sol and proteins, sulphur sol forms multimolecular colloids.
Sulphur sol consists of particles containing a thousand or more S8 molecules. On
the other hand, proteins form macromolecular colloids.
Answer15: (i) Zone refining method is the most suitable method for refining metals like
germanium (semiconductor).
(ii) In the extraction of aluminium, impure Al2O3 is dissolved in
concentrated NaOH to form NaAlO2. This method is known as leaching of alumina.
Al2O3 ( s ) + 2 NaOH ( aq ) + 3 H 2O ( l ) 2 Na Al ( OH )4 ( aq )
(iii) Coke reduces the iron oxide to molten iron metal. Also, coke, when burnt in the
blast furnace, supplies the heat required for carrying out the extraction of iron
from its oxide.
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FeO + C Fe + CO
Answer16: The balanced chemical reaction can be written as follows:
2 Cr ( s ) + 3 Fe2 + ( 0.1 M )
2 Cr 3 + ( 0.01 M ) + 3 Fe ( s )

Given :
Ecro 3+ / Cr = 0.74V
o
EFe
= 0.44V
2+
/ Fe

The cell can be represented as follows:

CrCr 3+ ( 0.01 M )Fe 2 + ( 0.1 M )Fe ( s )
o
can be calculated as follows:
ECell

0
o
o
Ecell
= EFe
ECr
2+
3+
/ Fe
/ Cr

o
Ecell
= 0.44 ( 0.74 ) = 0.30V
2

Ecell = E

o
cell

Cr 3+
2.303 RT

log
3
nF
Fe 2+

( 0.01)
0.0591
ECell = 0.30
log
3
6
( 0.1)

ECell = 0.30 + 0.01

ECell = 0.31V
Answer17: (i) Mn shows the highest oxidation state of +7 with oxygen because it can form
ppidpi multiple bonds using 2p orbital of oxygen and 3d orbital of Mn. On the
other hand, Mn shows the highest oxidation state of +4 with flourine because it
can form single bond only.
(ii) The variable oxidation states of transition elements are due to the participation
of ns and (n1)d-electrons in bonding. Lower oxidation state is exhibited when
the ns-electrons take part in bonding. Higher oxidation states are exhibited when
the (n 1)d-electrons take part in bonding.
(iii) Actinoids show irregularities in their electronic configurations because the
energy differences between 5f, 6d and 7s subshells are very small; hence, an
electron can be occupied in any of the subshells. They have the electronic
configuration of 7s2 with variation of occupancy in 5f and 6d orbitals.
Answer18: (i)

(ii)
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(iii)

Answer19: (i)

(ii)

Answer20: (i) In polymerisation of ethene, source of free radical is needed to initiate the
chain reaction. Such free radicals are usually produced by decomposition of
peroxides like t-butyl peroxide or benzoyl peroxide.
(ii) The given polymer is nylon 6, 6.
Monomers of nylon 6, 6 are adipic acid (HOOC(CH2)4COOH) and
hexamethylenediamine (H2N(CH2)6NH2).
(iii) Elastomers of rubbers have the weakest intermolecular forces of
attraction, while fibres have the strongest intermolecular forces of attraction.
Plastics have intermdiate forces of attraction.
The increasing order of intermolecular forces of attraction of the given polymers
is as follows: Terylene> Polystyrene > Buna-S
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Or
Free radical mechanism for polymerisation of ethane
Chain-initiating step

Chain-propagating step

Chain-terminating step

Answer21: (i) Upon hydrolysis, lactose produces one molecule of D-glucose and one molecule
of D-galactose.
(ii) Vitamin C is water-soluble in nature. It cannot be stored in the human body as it
repeatedly gets eliminated through urine.
(iii) A nucleoside is formed by the attachment of purine or pyrimidine base to the 1position of a pentose sugar.
On the other hand, a nucleotide is a unit formed by the attachment of nucleoside
to phosphoric acid at the 5-position of the sugar moiety.

Answer22: (a)

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Hybridisation: d2sp3
Magnetic character: Paramagnetic
Spin nature of complex: Low-spin complex
(b) cis-isomer of [Pt(en)2Cl2]2+ is optically active.

Section D
Answer23: (i) The following values are displayed by Mr. Deepak:
(a) Care and concern: He cared for the well-being of his friend Mr. Angad.
(b) Knowledge: He suggested his friend effective measures to counter stress and
anxiety.
(ii) Sleeping pills are prescribed by doctors to patients in stress, pain or depression.
It should not be taken without a prescription or a doctor's consultancy because
these pills have several side effects. Sleeping pills slow down the functioning of
the brain and the nervous system.
(iii) Tranquillisers are those class of organic compounds that are neurologically
active drugs. They perform their function by inhibiting the message transfer
mechanism from nerve to receptor. They induce a sense of well-being and are
used in the treatment of stress, anxiety, irritability and mental diseases. Their
examples are chlordiazepoxide, iproniazid, phenelzine, meprobamate and
equanil.
Section E
Answer24: (a) (i) Ozone decomposes into O2 with the evolution of heat, i.e. H is negative
(exothermic). O3 O2 + O
H = negative
Since the decomposition of O3 increases the number and freedom of particles,
entropy also increases.
Therefore, S = positive
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Now, G = H TS
Both H and T S (since S is positive) result into large negative G. Hence,
O3 becomes thermodynamically unstable and decomposes into oxygen easily.
(ii) PCl5 is ionic in solid state because it exists as [PCl4]+ [PCl6] in which the cation
has tetrahedral geometry and the anion has octahedral geometry.
(b) (i) BrF5
(ii) XeF4
OR
(i) Although electron gain enthalpy of fluorine is less than that of chlorine because of
the small size of fluorine, but the oxidising power depends on other factors
like bond dissociation energy and hydration energy. The smaller the size of the
atom, the greater the hydration enthalpy. Fluorine being small in size has higher
hydration enthalpy as compared to chlorine. Also, fluorine faces greater interelectronic repulsion among its lone pairs of electrons because of its small size,
while there is very less repulsion in chlorine. Hence, the bond dissociation
enthalpy of fluorine is lower than that of chlorine.
Thus, the high hydration enthalpy and low bond dissociation enthalpy of fluorine
result in its higher oxidising power as compared to that of chlorine.
(ii) Manufacturing of sulphuric acid via the contact process involves three steps:
(1) Burning of ores to form SO2
(2) Conversion of SO2 to SO3 using V2O5 as a catalyst
(3) Absorption of SO3 in H2SO4 to give oleum
The second step, i.e. conversion of SO2 to SO3 is the key step. Since this reaction is
exothermic in nature and two moles of gaseous reactant give one mole of gaseous
product. Thus, in accordance with Le Chatelier's principle, to obtain the maximum
amount of SO3, low temperature and high pressure are required.
(iii) (a) Reducing character: H3PO4< H3PO3< H3PO2
This trend can be explained on the basis of structures of oxyacids of phosphorus.
The higher the number of PH bond, the higher the reducing power of the oxyacid
of phosphorus. There are two PH bonds in H3PO2, one PH bond in H3PO3 and
no PH bond in H3PO4. So, this explains the reducing trend of the given oxyacids
of phosphorus.
(b) Base strength: BiH3< SbH3< PH3< NH3
On moving down the group, the size of the central atom increases. This decreases
the electron density on the central atom and thereby affecting the electrondonating ability of the atom. Hence, the basic strength decreases on moving down
the group.
Answer25:

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OR
(a) Cannizzaro reaction

(b) Semicarbazone of ethanol

(c) Fluorine is more electronegative than chlorine. The presence of fluorine in a

molecule will make it more acidic. Thus, the pKa of FCH2COOH is lower than that
of ClCH2COOH.
( i ) DIBAL H CH CH = CH CH CHO
(d) CH 3 CH = CH CH 2CN
3
2
( ii ) H 2O
(e)
Propanal

Propanone

It forms silver mirror on reaction with

Tollen's reagent.

It is not oxidised by Tollen's reagent.

It does not react with iodoform.

It gives positive iodoform test.

On reacting with Schiff's reagent, it gives

pink colour.

It does not react with Schiff's reagent.

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Answer26: (a) Given:

K f =1.86 K kg mol 1
Mass of solute =1.9 g
Mass of solvent = 50 g
Therefore,
Molality of the solution, m = m =

1.9 10000

95
50

m = 0.4 m
Also, MgCl2 undergoes complete ionisation and thereby yielding 3 moles of
constituent ions for every mole of MgCl2.
i=3
Now, depression in freezing point is given as
Tf = iK f m
= 3 1.86 0.4
= 2.232 K
T f = 273.15 2.232
= 270.918 K
Hence, the new freezing point of the solution is 270.92 K.
(b) (i) The elevation in the boiling point of a solution is a colligative property;
therefore, it is affected by the number of particles of the solute. Since the amount
of solute is higher in 2 M glucose solution as compared to 1 M glucose solution,
the elevation in the boiling point is higher. Hence, 2 M glucose solution has a
higher boiling point than 1 M glucose solution.
(ii) When the external pressure exerted on the solution is higher than the osmotic
pressure, the pure solvent starts flowing out of the solution through the semipermeable membrane. This process is known as reverse-osmosis.
OR
(a) Given:
K f = 3.83 K kg mol 1

Mass of solute = 2.56 g

Mass of solvent =100 g
Therefore,
Molality of the solution, m = m =

2.56 1000

32 100

m = 0.8 m
The depression in freezing point of a solution is given as

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T f = iKfm
0.383 = i 3.83 0.8
1
i=
8
Hence, 8 sulphur atoms are undergoing association, as shown below:
8S S8
(b) (i) 1.2% sodium chloride solution is hypertonic wrt 0.9% sodium chloride
solution. Therefore, when the blood cells are placed in 1.2% sodium chloride
solution, water flows out of the cells and the cells shrink.
(ii) 0.4% sodium chloride solution is hypotonic wrt 0.9% sodium chloride solution.
Therefore, when the blood cells are placed in 0.4% sodium chloride solution,
water flows into the cells and the cells swell.

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