CHEMISTRY

SOLUTION : PRACTICE PAPER – 4

SECTION – A
Q. 1. (i) (c) 0
(ii) (c) 32%
(iii) (b) anomeric hydroxyl group
(iv) (a) 43.4 kJ mol 91
(v) (a) nature of solvent
(vi) (d) All of the above
(vii) (d) cellulose
(viii) (d) Paul T. Anastas
(ix) (d) 75 mL of 0.2M HCl;25 mL of 0.2 M NaOH
(x) (a) 2° amine
Q. 2. (i) Cell constant of a conductivity cell is defined as the ratio of the distance between
the electrodes divided by the area of cross section of the electrodes.
(ii) The inner shell electrons in an atom screen or shield the outermost electron from
nuclear attraction. This effect is called shielding effect.
The magnitude of shielding effect depends upon the number of inner electrons.
(iii)

Cis – Diamminebromochloroplatinum(II) Trans – Diamminebromochloroplatinum(II)

(iv) Given : x :0.05


P:2;10 Nm92
P :?

B x ;x :1
 
 x :19x :190.05:0.95
 
P P 2;10
:x P : : :2.105;10 Nm 92
P   x 0.95
 
Ans. Vapour pressure of a pure solvent:P :2.105;10 Nm 92.

(v) Bromine reacts instantly with magnesium metal to give magnesium bromide.
Mg(s) ;Br (l) MgBr (s)
 
IIIIJ

Magnesium bromide

(vi) CH –CH 9CH

  
OH
(vii) The aqueous solution of formaldehyde (40%) is known as formalin.
SOLUTIONS TO NAVNEET PRACTICE PAPERS : STD. XII 1
 (viii) Enthalpy of atomisation (atmH) : It is the enthalpy change accompanying the
dissociation of one mole of gaseous substance into its atoms at constant
temperature and pressure.
For example : CH (g) ; C(g) ;4H(g) atomH:1660 kJ mol\

SECTION – B
Q. 3. (1) Interhalogen compounds : Compounds formed by the combination of atoms of
two different halogens are called interhalogen compounds. In an interhalogen
compound, of the two halogen atoms, one atom is more electropositive than the
other. The interhalogen compound is regarded as the halide of the more electroposi-
tive halogen.
For example ClF, BrF , ICl

(2) Chlorine trifluoride, ClF : It is a colourless gas, obtained by reacting Cl with
 
excess of F .

Cl ;3F 2ClF
  
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excess

Q. 4. Consider a certain amount of an ideal gas enclosed in an ideal cylinder fitted with
massless, frictionless rigid movable piston at pressure P, occupying volume V at

temperature T.

Fig. : Work of expansion

As the gas expands, it pushes the piston upward through a distance d against external
force F, pushing the surroundings.
The work done by the gas is,
W:opposing force;distance
: 9F;d
9ve sign indicates the lowering of energy of the system during expansion.
If a is the cross section area of the cylinder or piston, then,
F
W: 9 ;d;a
a
F
Now the pressure is Pex :
a
while volume change is, V:d;a
 W: 9Pex ;V
2 SOLUTIONS TO NAVNEET PRACTICE PAPERS : STD. XII
 If during the expansion, the volume changes from V and V then, V:V 9V
   
 W: 9Pex (V 9V )
 
During compression, the work W is ;ve, since the energy of the system is increased,
W: ;Pex (V 9V )
 
Q. 5. (1) Cis-isomer : A heteroleptic coordination compound in which two similar ligands
are arranged adjacent to each other is called cis-isomer.
For example, Cis-Diamminedichloroplatinum(II)

(2) Trans-isomer : A heteroleptic coordination compound in which two similar ligands

are arranged diagonally opposite to each other is called trans-isomer.
For example, Trans-Diamminedichloroplatinum(II)

Q. 6. (a) I ;KClO ICI;KIO

  
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(b) BrCl;H O HOBr;HCl


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Q. 7. Principles of green chemistry :

(1) Role of real time analysis in pollution prevention :
(i) There is a dire need to develop improvised analytical methods to allow for real
time, in process monitoring and control prior to the formation of hazardous
substances.
(ii) It is very much important for the chemical industries and nuclear reactors to
develop or modify analytical methodologies so that continuous monitoring of
the manufacturing and processing unit is possible.
(2) Role of safer chemistry in accident prevention :
(i) It is needed to develop chemical processes that are safer and minimize the risk
of accidents. It is important to select chemical substances used in a chemical
reaction in such a way that they can minimize the occurrence of chemical
accidents, explosions, fire and emissions.
(ii) For example : Chemical process that works with the gaseous substances can
lead to relatively higher possibilities of accidents including explosion as
compared to the system working with nonvolatile liquid and solid substances.
SOLUTIONS TO NAVNEET PRACTICE PAPERS : STD. XII 3
Q. 8. (a) Overall reaction :
2NO(g) ;Cl (g) 2NOCl(g)

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(b) NOCl (g) is a reaction intermediate.


Q. 9. A:C H CH CN
  
Phenyl acetonitrile
B:C H CH CH NH
    
-phenyl ethyl amine

3.8;10\
Q. 10. Given : Required concentration of O :3.8 mg/L: mol L\
 32
Solubility of O :2.2;10\ mol L\

P:1 atm
Partial pressure of O needed:Po :?
 
S:KH ;Po

S 2.2;10\
 KH : : :2.2;10\ mol L\ atm\
Po 1

S 3.8;10\ 1
 Po : : ; :0.05397 atm
 KH 32 2.2;10\
Ans. Pressure needed:Po :0.05397 atm.

Q. 11. Preparation of phenol from benzene sulphonic acid : Benzene sulphonic acid is
neutralized with the requisite quantity of soda ash (Na CO ) or NaOH and the solution
 
is evaporated to obtain sodium benzene sulphonate salt. Dry sodium benzene
sulphonate is fused with an excess of caustic soda (NaOH) at about 573 K when sodium
phenoxide is formed. The fused mass of sodium phenoxide on treatment with dilute
HCl gives phenol.

4 SOLUTIONS TO NAVNEET PRACTICE PAPERS : STD. XII

Q. 12. (i) Consider representation of Daniell cell,

Zn(s)  Zn> 1M  Cu> 1M  Cu(s)

Single vertical line represents separation of two phases, solid Zn(s) and solution of
ions.

(ii) Double vertical lines represent a salt bridge.

Q. 13.

Globular proteins Fibrous proteins

(1) The chains of polypeptides of protein (1) The proteins in which the polypeptide
coil around to give a spherical shape. chains lie parallel to form fibre like
structure.
(2) Globular proteins are soluble in water. (2) Fibrous proteins are insoluble in water.
(3) They are sensitive to small changes of (3) They are stable to moderate changes of
temperature and pH. temperature and pH.
(4) They possess biological activity. (4) They do not possess biological activity.

Q. 14. Given : [OH\]:2.87;10\ M, pH:?

pOH:9log [OH\]

:9log 2.87;10\

:9(4.4579)
:(490.4579)
:3.5421
B pH;pOH:14
 pH:149pOH:1493.5421:10.4579
Ans. pH:10.4579.
SECTION – C

cold
Q. 15. (a) Cl ;2NaOH NaCl; NaOCl ; H O
 
IIIIIIJ

dil. Sodium
hypochlorite
hot
(b) Cl ;6NaOH 5NaCl;NaClO ; 3H O
  
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conc. Sodium
chlorate
(c) When chlorine is passed over dry slaked lime Ca(OH) , bleaching powder, CaOCl
 
is obtained.
Ca(OH) ;Cl CaOCl ;H O
   
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SOLUTIONS TO NAVNEET PRACTICE PAPERS : STD. XII 5

Q. 16. (1) Aldehydes which do not have -hydrogen atom, on heating with concentrated
alkali (50% aqueous or ethanolic solution of NaOH or KOH) undergo self
oxidation and reduction reaction or redox reaction.
(2) This self redox reaction or disproportionation reaction is called Cannizzaro
reaction.
(3) In this reaction one molecule of the aldehyde is oxidised to carboxylic acid while
the second molecule of the aldehyde is reduced to alcohol (carboxylic acid formed,
reacts with alkali, NaOH and forms a salt R9COONa).
(4) When formaldehyde (methanal) is heated with 50% NaOH solution, methanol
(reduction product) and sodium formate (oxidation product) are formed.
O O  O
H9C ; H9C ; NaOH H9C 9 ; ; CH 9OH

IIIIIIIJ

H H O Na
(50%)
Methanal Methanal Sodium formate Methanol

Similarly, benzaldehyde gives Cannizzaro reaction.

O O  O
C H 9C ; C H 9C ; NaOH C H 9C 9 ; ; C H 9CH OH
        
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H H O Na
(50%)
Benzaldehyde Benzaldehyde Sodium benzoate Benzyl alcohol

(5) Ketones and aldehydes like acetaldehyde, propionaldehyde, etc. having 9H
atom do not give Cannizzaro reaction.
Q. 17. (a) (1) Unit cell : It is the smallest repeating structural unit of a crystalline solid
(or crystal lattice) which when repeated in different directions produces the
crystalline solid (lattice).
(2) The crystal is considered to consist of an infinite number of unit cells.
(3) The unit cell possesses all the characteristics of the crystalline solid.
(b) (1) ECa>/ Ca :92.866 V and ECd>/  Cd :90.403 V
Since, ECa>/ Ca  ECd>/ Cd, Ca will reduce Cd>
(aq) and reaction would occur.

 Br\ :;1.080 V and ESn>/

(2) EBr/  Sn :90.136
B ESn>/ Sn  EBr/ Br\ , reaction will not occur.
Possible reaction is,
Br (l) ;Sn(s) \ ;Sn>
2Br(aq)
 (aq)
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Q. 18. (a) Conjugate acid-base pair : A pair of an acid and a base differing by a proton is
called a conjugate acid-base pair.
HCl(aq) ; H O(l) & H O> ;Cl\
  (aq) (aq)

Acid 1 Base 2 Acid 2 Base 1

C

C!------!C

!
conjugate acid-base pair 2
---------------- !

conjugate acid-base pair 1

6 SOLUTIONS TO NAVNEET PRACTICE PAPERS : STD. XII

 (b) The ionic product of water, Kw is given by,
Kw :[H O>];[OH\]

At 298 K, Kw :1;10\
 pKw :9log Kw :9log 1;10\:14
 
B [H O>];[OH\]:1;10\

Taking logarithm to base 10 of both sides,
log [H O>];log [OH\]:log 1;10\
   
Multiplying both the sides by 91,
9log [H O>]9log [OH\]:9log 1;10\
   
B pH:9log [H O>]; pOH:9log [OH\];
  
pKw :9log Kw

 pH;pOH:pKw
OR pH;pOH:14

Q. 19. (1) Diethyl ether on hydrolysis give ethanol.

dil. H SO
C H –O–C H ;H O   2C H –OH
      
IIIIIIIIIIIIIIIIJ

heat, pressure
Diethyl ether Ethanol

(2) A mixed ether on heating with dil. H SO under pressure undergoes hydrolysis to
 
give mixture of two different alcohols.
dil. H SO
R–O–R;H O   R–OH;R–OH

IIIIIIIIIIIIIIIIIIIIIIJ

heat under pressure

Ethyl methyl ether on hydrolysis give a mixture of ethanol and methanol.

dil. H SO
C H –O–CH ;H O   C H –OH;CH –OH
      
IIIIIIIIIIIIIIIIIIIIIIJ

heat under pressure

Ethyl methyl ether Ethanol Methanol

(3) Anisole on hydrolysis give a mixture of phenol and methanol.

Q. 20. Given :
Zn(s)  Zn> (0.2 M) H> (1.6 M)  H (g, 1.8 atm)  Pt


EZn>/Zn :90.763 V; [Zn>]:0.2 M;
[H>]:1.6 M; PH :1.8 atm; Ecell :?


SOLUTIONS TO NAVNEET PRACTICE PAPERS : STD. XII 7

 Cell reaction :
(LHE) Zn(s) IIIIIJ Zn>
(aq) ;2e\ (oxidation)
2H>
(aq) ;2e\ H (g) (reduction)

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Zn(s) ;2H> Zn>

(aq) ;H (g) overall reaction
(aq)

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(1.6 M) (0.02 M) 1.8 atm

 n:2
0.0592 [Zn>];[H ]
Ecell :Ecell 9 log 
n  [H>]
Now, Ecell :EH>/H 9EZn>/Zn

:0.09(90.763)
:;0.763 V
Since [H ]:PH :1.8 atm,
 
0.0592 0.2;(1.8)
 Ecell :0.7639 log
2  (1.6)
:0.76390.0296 log 0.1406

:0.76390.0296 (1.1479)
:0.76390.0296;(90.8521)
:0.763;0.02522
:0.7882 V
Ans. Ecell :0.7882 V

Q. 21. (i) (a) ClO is used as a bleaching agent in paper industry.


(b) It is used in water treatment.

(ii) Ozone reduces hydrogen peroxide, H O to water, H O.

  
H O ;O H O;2O
    
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(iii) Concentrated sulphuric acid when added to sugar, it is dehydrated giving carbon.
conc. H SO
C H O   12C;11H O.
   
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Q. 22. (1) Vinyl halide

(2) C9X bond length shorter in vinyl halide than alkyl halide. Vinyl halide has partial
double bond character due to resonance.
In vinyl halide, carbon is sp hybridised. The bond is shorter and stronger and the
molecule is more stable.
(3) Yes, it reacts by SN1 mechanism. SN1 mechanism involves formation of carboca-
tion intermediate. The vinylic carbocation intermediate formed is resonance
stabilized, hence SN mechanism is favoured.
8 SOLUTIONS TO NAVNEET PRACTICE PAPERS : STD. XII
Q. 23. Solution : n:0.4 mol
Number of octahedral voids:?
Number of tetrahedral voids:?
Number of atoms:n ;6.022;10
:0.4;6.022;10
:2.4088;10
(a) Number of octahedral voids:2.4088;10
(b) Number of tetrahedral voids:2;2.4088;10
:4.8176;10
(c) Total voids formed in 0.4 mol of it:7.2264;10
Ans. (a) 2.4088;10
(b) 4.8176;10
(c) 7.2264;10

Q. 24. (1) Hexaamminecobalt(III) ion, [CO(NH ) ]> is a cationic complex, the oxidation

state of cobalt is ;3 and the coordination number is 6.
(2) Electronic configuration : Co [Ar] 3d 4s

Electronic configuration : Co> [Ar] 3d 4s 4p

3d 4s 4p

Co> (Ground state)

(3) Since NH is a strong ligand, due to spin pairing effect, all the four unpaired

electrons in 3d orbital are paired giving two vacant 3d orbitals.

3d 4s 4p

Co> (Excited state)
ZIIIII dsp hybridisation IIIIIJ

(4) Since the coordination number is 6, Co> ion gets six vacant orbitals by
hybridisation of two 3d vacant orbitals, one 4s and three 4p orbitals forming six
dsp hybrid orbitals giving octahedral geometry. It is an inner complex.
Co>
3d dsp hybrid orbitals

(5) 6 lone pairs of electrons from 6NH ligands are accommodated in the six vacant

dsp hybrid orbitals. Thus six hybrid orbitals of Co> overlap with filled orbitals
of NH forming 6 coordinate bonds giving octahedral geometry to the complex.

Co> NH NH NH NH NH NH
     
[Co(NH ) ]> ;; ;; ;; ;; ;; ;;

3d dsp hybrid orbitals
SOLUTIONS TO NAVNEET PRACTICE PAPERS : STD. XII 9
 Since the complex has all electrons paired, it is diamagnetic.

[Co(NH ) ]>


Fig. : Structure of [Co(NH ) ]>



Complex Hybridisation Geometry Magnetic property

[Co(NH ) ]> dsp (inner) Octahedral Diamagnetic (
:0)


Q. 25. Pseudo first order reaction : A reaction which has higher order true rate law but
experimentally found to behave as first order is called pseudo first order reaction.
Explanation : Consider an acid hydrolysis reaction of an ester like methyl acetate.
H;(aq)
CH COOCH (aq) ;H O(l) CH COOH(aq) ;CH OH(aq)
   IIIIIIJ

 
Since the reaction involves two substances, ester and water, it is a bimolecular reaction
and the true rate law should be,
Rate:k [CH COOCH ];[H O]
  
Hence the reaction is expected to follow second order kinetics. However experimen-
tally it is found that the reaction follows first order kinetics.
This is because solvent water being in a large excess, its concentration remains
constant. Hence, [H O]:constant:k

Rate:k [CH COOCH ];[H O]
  
: k [CH COOCH ];k
 
:k;k;[CH COOCH ]
 
If k;k:k, then Rate:k [CH COOCH ]. This indicates that second order true rate
 
law is forced into first order rate law. Therefore this bimolecular reaction which
appears of second order is called pseudo first order reaction.
Q. 26. (i) Reducing sugars : Carbohydrates which reduce Fehling solution to red ppt of
Cu O or Tollen’s reagent to shining metallic silver are called reducing sugars.

All monosaccharides and oligosaccharides except sucrose are reducing sugars.
(ii) The order of basicity of aliphatic alkyl amines in the gaseous follows the order :
tertiary amine  secondary amine  primary amine  NH .

(iii) Cationic sphere complexes : A positively charged coordination sphere or a
coordination compound having a positively charged coordination sphere is called
cationic sphere complex.
For example : [Zn(NH ) ]> and [Co(NH ) Cl]SO are cationic complexes. The
  
latter has coordination sphere [Co(NH ) Cl]>, the anion SO \ makes it
 
electrically neutral.
10 SOLUTIONS TO NAVNEET PRACTICE PAPERS : STD. XII
 SECTION – D
Q. 27. (a) (i) Definition : The osmotic pressure is defined as the excess mechanical
pressure required to be applied to a solution separated by a semipermeable
membrane from pure solvent or a dilute solution to prevent the osmosis or free
passage of the solvent molecules at a given temperature. The osmotic pressure
is a colligative property.
(ii) Statement of Raoult’s law : The law states that the vapour pressure of a
solvent over the solution of a nonvolatile solute is equal to the vapour pressure
of the pure solvent multiplied by mole fraction of the solvent at constant
temperature.
(b) Given : WCu :2.4 g; t:1 hr:1;60;60 s
MCu :63.5 g mol\; I:?
Cu>(aq) ; 2e\ IIIIIJ Cu(s)
mole of Cu 1
Mole ratio: :
mole of electrons 2
I;t
WCu : ;mole ratio;molar mass of Cu
96500
WCu ;96500
 I:
t;mole ratio;molar mass of Cu
2.4;96500
:
1
1;60;60; ;63.5
2
:2.026 A
Ans. Current strength:I:2.026 A
Q. 28. (1) Acetone : Acetonitrile (ethanenitrile) reacts with methyl magnesium iodide in
presence of dry ether to give imine complex which on hydrolysis gives acetone.
During reaction acetonitrile and methyl magnesium iodide should be taken in
equimolecular proportion.
;
dry ether H O
H C9C Y N;CH MgI CH 9C: NMgI 
   
IIIIIIIIIIIJ IIIIIIIIIJ

H C

CH 9CO9CH ;NH ;Mg(I)OH
  
Acetone
(2) Benzophenone : Benzonitrile reacts with phenyl magnesium bromide in presence
of dry ether to give an imine complex which on acid hydrolysis gives a
benzophenone. During reaction benzonitrile and phenyl magnesium bromide
should be taken in equimolecular proportion.

SOLUTIONS TO NAVNEET PRACTICE PAPERS : STD. XII 11

Q. 29. (i) Consider alkaline hydrolysis of tert-butyl bromide (2-Bromo-2-methylpropane)
with aqueous NaOH or KOH.
CH CH
   
CH – C – Br ; OH9 CH – C – OH ; Br9
   
IIIIIIJ

CH CH
 
tert-butyl bromide nucleophile tert-butyl alcohol
(substrate)

(ii) Kinetics of the reaction : Due to steric hindrance of voluminous three methyl
groups around carbon, nucleophile OH9 cannot attack carbon atom directly.
Hence, the reaction takes place in two steps.
Step I : This involves heterolytic fission of C9Br covalent bond in the substrate
forming carbocation and Br9. This is a slow process.
CH CH
  slow  
CH – C – Br CH – C ; ; Br9
  RDS  
CH CH
 
Carbonium ion

Step II : This step involves attack of nucleophile OH9 or carbocation forming

C9OH bond and product tert-butyl alcohol. Since it involves ionic charge
neutralisation, it is a fast step.
CH CH
  fast  
; 9
CH – C ; OH CH – C – OH
   
IIIIIIJ

CH CH
 
Rate Determining Step (R.D.S.) : Since the first step is a slow step, it is
R.D.S., and therefore the rate of the reaction depends on the concentration of only
one reactant, (CH ) C9Br.

Rate:R:k [(CH ) C9Br] where k is a rate constant of the reaction.

SN reaction : The reaction between tert.butyl bromide and hydroxide ion to
form tert.butyl alcohol follows a first – order kinetics. The rate of this reaction
depends only on the concentration of one substance (tert-butyl bromide) and is
independent of concentration of alkali added. It is unimolecular first (1st) order
Nucleophilic Substitution reaction denoted as SN reaction.
Stereochemistry and mechanism of the reaction : The reaction takes place
in two steps and both the steps involve formation of transition states (T.S.).

12 SOLUTIONS TO NAVNEET PRACTICE PAPERS : STD. XII

 T.S. – I for first step :

Fig. : Formation of carbocation intermediate

In this transition state, C9Br bond is partially broken, so that carbon atom carries
partial positive charge (; ) and Br carries partial negative charge (9 ) which
further breaks forming carbocation and Br9. Tert-butyl cation (carbocation) has a
planar structure and the CH –C–CH bond angle is 120°. It is the intermediate of
 
the reaction. It is unstable. In this step, hybridisation of carbon atom changes from
sp (tetrahedral geometry) to sp (planar geometry).
T.S. – II for second step :

Fig. : SN mechanism

In this transition state, C9OH bond is partially formed so that carbon atom carries
partial positive charge (; ) and OH carries partial negative charge (9 ) which
further forms tert-butyl alcohol.
Formation of a racemic mixture : Since OH9 has equal probability of the
attack on carbocation from frontside and from backside, the products obtained are
equal. In case of optical active alkyl halide, a racemic mixture is obtained.
9
Q. 30. (a) (i) Co2; [Ar] 3d

(ii) For a zero order reaction : The rate of reaction is R:k [A]:k
Hence, the velocity constant k has the unit of the rate of the reaction,
i.e., mol dm 93 s 91.
> >
(b) (i) Chlorous acid, HClO (ii) Perchloric acid, HClO
 

SOLUTIONS TO NAVNEET PRACTICE PAPERS : STD. XII 13

Q. 31. (i) Synthetic resins are artificially synthesised high molecular weight polymers. They
are the basic raw material of plastic. The main properties of plastic depend on the
synthetic resin it is made from.
Examples of natural resins : Rosin, Damar, Copal, Sandarac, Amber, Manila
Examples of synthetic resins : Polyester resin, Phenolic resin, Alkyl resin,
Polycarbonate resin, Polyamide resin, Polyurethane resin, silicone resin, Epoxy
resin, Acrylic resin.
Formula weight of the desired product
(ii) % atom economy: ;100
Sum of formula weight of all the
reactants used in the reaction

14 SOLUTIONS TO NAVNEET PRACTICE PAPERS : STD. XII