Examination Paper of CBSE CLass XII
Examination Paper of CBSE CLass XII
Examination Paper of CBSE CLass XII
Examination Papers
2008–2014
CONTENT
n CBSE Examination Paper–2008 (Delhi) 3
n CBSE Examination Paper–2008 (All India) 23
n CBSE Examination Paper–2009 (Delhi) 43
n CBSE Examination Paper–2009 (All India) 69
n CBSE Examination Paper–2009 (Foreign) 92
n CBSE Examination Paper–2010 (Delhi) 116
n CBSE Examination Paper–2010 (All India) 134
n CBSE Examination Paper–2010 (Foreign) 152
n CBSE Examination Paper–2011 (Delhi) 171
n CBSE Examination Paper–2011 (All India) 191
n CBSE Examination Paper–2011 (Foreign) 209
n CBSE Examination Paper–2012 (Delhi) 229
n CBSE Examination Paper–2012 (All India) 249
n CBSE Examination Paper–2012 (Foreign) 267
n CBSE Examination Paper–2013 (Delhi) 285
n CBSE Examination Paper–2013 (All India) 300
n CBSE Examination Paper–2013 (Foreign) 315
n CBSE Examination Paper–2014 (Delhi) 331
n CBSE Examination Paper–2014 (All India) 349
n CBSE Examination Paper–2014 (Foreign) 367
CBSE EXAMINATION PAPERS
DELHI—2008
Time allowed: 3 hours Maximum marks: 70
General Instructions:
(i) All questions are compulsory.
(ii) Question nos. 1 to 8 are very short answer questions and carry 1 mark each.
(iii) Question nos. 9 to 18 are short answer questions and carry 2 marks each.
(iv) Question nos. 19 to 27 are also short answer questions and carry 3 marks each.
(v) Question nos. 28 to 30 are long answer questions and carry 5 marks each.
(vi) Use log tables if necessary, use of calculators is not allowed.
13. What is meant by the ‘rate constant, k’ of a reaction? If the concentration is expressed in mol L-1
units and time in seconds, what would be the units for k (i) for a zero order reaction and (ii) for a
first order reaction?
14. Define the following terms in relation to proteins:
(i) Peptide linkage (ii) Denaturation
15. List the reactions of glucose which cannot be explained by its open chain structure.
16. Assign a reason for each of the following statements:
(i) Ammonia is a stronger base than phosphine.
(ii) Sulphur in vapour state exhibits a paramagnetic behaviour.
17. Draw the structure of the following molecules:
(i) SF4 (ii) XeF4
18. What are biodegradable and non-biodegradable detergents? Give one example of each class.
19. What is a semiconductor? Describe the two main types of semiconductors and explain mechanisms
for their conduction.
20. Calculate the temperature at which a solution containing 54 g of glucose, (C 6 H12 O6 ), in 250 g of
water will freeze. (K f for water = 1.86 K mol -1 kg)
21. What are lyophilic and lyophobic sols? Give one example of each type. Which one of these two
types of sols is easily coagulated and why?
22. State briefly the principles which serve as basis for the following operations in metallurgy:
(i) Froth floatation process
(ii) Zone refining
(iii) Refining by liquation
23. Write chemical equations for the following processes:
(i) Chlorine reacts with a hot concentrated solution of sodium hydroxide.
(ii) Orthophosphorous acid is heated
(iii) PtF6 and xenon are mixed together.
OR
Complete the following chemical equations:
(i) Ca 3 P2 ( s) + H2 O (l) ¾¾® ¼
(ii) Cu 2+ ( aq) + NH3 ( aq) ¾¾® ¼
(excess)
(iii) F2 ( g) + H2 O (l) ¾¾® ¼
24. (a) What is a ligand? Give an example of a bidentate ligand.
(b) Explain as to how the two complexes of nickel, [Ni (CN) 4 ] 2- and Ni (CO) 4 , have different
structures but do not differ in their magnetic behaviour. (Ni = 28)
25. Name the reagents which are used in the following conversions:
(i) A primary alcohol to an aldehyde
(ii) Butan-2-one to butan-2-ol
(iii) Phenol to 2, 4, 6-tribromophenol
26. Account for the following observations:
(i) pK b for aniline is more than that for methylamine.
(ii) Methylamine solution in water reacts with ferric chloride solution to give a precipitate of ferric
hydroxide.
(iii) Aniline does not undergo Friedel-Crafts reaction.
Examination Papers | 5
27. Write the names and structure of the monomers of the following polymers:
(i) Buna-S (ii) Neoprene (iii) Nylon-6
28. Conductivity of 0.00241 M acetic acid solution is 7.896 ´ 10 -5 S cm -1 . Calculate its molar
conductivity in this solution. If L°m for acetic acid is 390.5 S cm 2 mol -1 , what would be its
dissociation constant?
OR
Three electrolytic cells A, B and C containing solutions of zinc sulphate, silver nitrate and copper
sulphate, respectively are connected in series. A steady current of 1.5 ampere was passed through
them until 1.45 g of silver were deposited at the cathode of cell B. How long did the current flow?
What mass of copper and what mass of zinc were deposited in the concerned cells? (Atomic
masses of Ag = 108, Zn = 65.4, Cu = 63.5)
29. Assign reasons for the following:
(i) The enthalpies of atomisation of transition elements are high.
(ii) The transition metals and many of their compounds act as good catalysts.
(iii) From element to element the actinoid contraction is greater than the lanthanoid contraction.
(iv) The E° value for the Mn 3+ / Mn 2+ couple is much more positive than that of Cr 3+ / Cr 2+ .
(v) Scandium ( Z = 21) does not exhibit variable oxidation states and yet it is regarded as a
transition element.
OR
(a) What may be the possible oxidation states of the transition metals with the following d
electronic configurations in the ground state of their atoms:
3d 3 4s 2 , 3d 5 4s 2 and 3d 6 4s 2 . Indicate relative stability of oxidation states in each case.
(b) Write steps involved in the preparation of (i) Na 2 CrO4 from chromite ore and (ii) K 2 MnO4
from pyrolusite ore.
30. (a) Complete the following reaction statements by giving the missing starting material, reagent or
product as required:
O2
(i) ........... ¾¾¾¾¾® 2 O
Zn ¾ H 2 O
.............
(ii) CH2 ¾¾¾¾® ¾ CHO
OR
(a) An organic compound contains 69.77% carbon, 11.63% hydrogen and the rest is oxygen. The
molecular mass of the compound is 86. It does not reduce Tollens’ reagent but forms an
addition compound with sodium hydrogen sulphite and gives positive iodoform test. On
vigorous oxidation it gives ethanoic and propanoic acids. Deduce the possible structure of the
organic compound.
(b) State reasons for the following:
(i) Monochloroethanoic acid has a higher pKa value than dichloroethanoic acid.
(ii) Ethanoic acid is a weaker acid than benzoic acid.
SOLUTIONS
CBSE (Delhi) SET–I
1. Coordination number of Na + ion = 6
Coordination number of Cl - ion = 6
2. The sum of powers of the concentrations of the reactants in the rate law expression is called the
order of reaction.
3. This is due to the unequal bombardment of colloidal particles by the molecules of dispersion
medium.
4. NO+2 has higher bond angle as the central atom nitrogen in NO-2 has a lone pair of electrons.
5. 2, 5-Dimethyl hexane-1, 3-diol.
6. (CH3 ) 2 CHCOOH < CH3 ¾ CH ¾ CH2 ¾ COOH < CH3 ¾ CH2 ¾ CH ¾ COOH
½ ½
Br Br
+
N2 Cl I
½ ½
D
7. + KI ¾¾¾® + KCl + N2
Benzene Iodobenzene
diazonium chloride
8. Phenol, 0.2% solution of phenol acts as antiseptic where as 1% solution acts as disinfectant.
9. In haloarenes C—X bond acquires a partial double bond character due to resonance. As a result
the bond cleavage in haloarenes is difficult than haloalkanes and therefore, they are less reactive
towards nucleophilic substitution reaction.
X +X +X + X X
| |
OR
(i) CH3–I reacts faster than CH3–Br as iodine is a better leaving group because of its larger size.
(ii) CH3–Cl (1° halide) reacts faster than (CH3 ) 3 CCl (3° halide) since in case tertiary butyl
chloride three bulky methyl group hinder the approaching nucleophile.
10. (a) 1-Bromo but-2-ene.
Peroxide
(b) CH3 - CH2 - CH = CH2 + H - Br ¾¾¾® CH3 - CH2 - CH2 - CH2 - Br
But-1-ene 1-bromo butane
11. It states that at constant temperature the mass of a gas(m) dissolved in a given volume of the
liquid is directly proportional to the pressure of the gas ( P) present in equilibrium with the liquid.
Examination Papers | 9
Mathematically, m µ P
or m = KH P
where K H is the Henry’s law constant.
Applications of Henry’s law are
(i) To increase the solubility of CO2 in soft drinks and soda water, the bottle is sealed under high
pressure.
(ii) To minimize the painful effects accompanying the decompression of deep sea divers, oxygen
diluted with less soluble helium gas is used as breathing gas.
12. For a first order reaction
2.303 [R ]0
K= log
t [R ]
[R ]0 100 10
when t = 40 minutes, = =
[ R ] 100 - 30 7
2.303 10 2.303 2.303
K= log = log 1.428 = ´ 0.1548
40 7 40 40
K = 8.91 ´ 10 - 3 min - 1
0.693 0.693
t 1/ 2 = =
K 8.91 ´ 10 -3
t 1/ 2 = 77.78 min.
13. Rate constant is the rate of the reaction when the concentration of each reactant is taken as unity.
Q rate = K [ A ] n
1- n
æ mol. ö
\ General unit of K = ç ÷ s -1
è lit. ø
(i) For a zero order reaction n = 0
\ Unit of K = mol lit -1 sec -1
(iii) For a first order reaction n = 1
\ Unit of K = sec - 1
14. (i) Peptide linkage: A peptide linkage is an amide linkage ( ¾ CONH ¾ ) formed between
¾ COOH group of one a-amino acid and NH2 group of the other amino acid by the elimination
of a water molecule.
O
½½ - H2O
H2 N ¾ CH2 ¾ C ¾ OH + H NH ¾ CH ¾ COOH ¾¾¾®
½
CH3
O
½½
H2 NCH2 ¾ C ¾ NH ¾ CH ¾ COOH
½
CH3
Peptide linkage
(Gly -Ala)
10 | Xam idea Chemistry–XII
(ii) Denaturation: When a protein in its native form is subjected to physical change like change in
temperature or chemical change like change in pH, the hydrogen bonds are disturbed. Due to
this, globules unfold and helix get uncoiled and proteins loses its biological activity. During
denaturation 2° and 3° structures of proteins are destroyed but 1° structure remains intact, e.g.,
coagulation of egg white on boiling.
15. The following reactions of glucose cannot be explained by its open chain structure.
(i) Despite having the aldehyde group glucose does not give 2, 4-DNP test, Schiffs test and it does
not form the hydrogen sulphite addition product with NaHSO3 .
(ii) The pentacetate of glucose does not react with hydroxylamine indicating the absence of free
—CHO group.
(iii) When D-glucose is treated with methanol in the presence of dry hydrogen chloride gas, it gives
two isomeric mono methyl derivatives known as a-D glucoside and methyl b-D glucoside.
These glucosides do not react with hydrogen cyanide or with hydroxylamine.
16. (i) As the atomic size of nitrogen is smaller than phosphorus, therefore electron density on
nitrogen atom is higher than that on phosphorus atom. Consequently the tendency of N in NH3
to donate its lone pair of electrons is much higher than that of P in PH3 . Thus, ammonia is
stronger base than phosphine.
(ii) In vapour state sulphur partly exists as S 2 molecule which has two unpaired electrons in the
antibonding p * orbitals like O2 and, hence exhibits paramagnetic behaviour.
17. (i) sp 3 d hybridisation. F
b. p. = 4
5e pairs S
l. p. = 1
F
See-saw shape
F
(ii) sp 3 d 2 hybridisation
F F
b. p. = 4 Xe
6e pairs
l. p. = 2 F F
Square planar
18. Biodegradable detergents: Detergents having straight hydrocarbon chains are easily degraded by
micro-organism and hence called biodegradable detergents, e.g., sodium–4–(1-dodecyl) benzene
sulphonate.
CH3 ¾ (CH2 ) 11 ¾ ¾ SO-3 Na +
Examination Papers | 11
Non-biodegradable detergents: Detergents having branched hydrocarbon chains are not easily
degraded by micro-organisms and hence are called non-biodegradable detergents, e.g., sodium-4-
(1, 3, 5, 7-tetramethyl octyl) benzenesulphonate.
CH3 CH3
½ ½
CH3 ¾ ( CH ¾ CH2 ¾ ) 3 ¾ CH ¾ ¾ SO-3 Na +
Non-biodegradable detergents accumulate in rivers and waterways thereby causing water pollution.
19. Semiconductor: These are the solids with conductivities in the intermediate range from 10 -6 to
10 4 ohm -1 m -1 .
Semiconductors are of two types
(i) n-type of semiconductors (ii) p-type of semiconductors
n-type semiconductor: When a silicon or germanium crystal is doped with group 15 element like
P or As, the dopant atom forms four covalent bonds like a Si or Ge atom but the fifth electron, not
used in bonding, becomes delocalised and contribute its share towards electrical conduction. Thus
silicon or germanium doped with P or As is called n-type semiconductor, n indicative of negative,
since it is the electron that conducts electricity.
p-type semiconductor: When silicon or germanium is doped with group 13 element like B or Al,
the dopant has only with three, valence electrons. An electron vacancy or a hole is created at the
place of the missing fourth electron. Here, this hole moves through the crystal like a positive
charge giving rise to electrical conductivity. Thus Si or Ge doped with B or Al is called p type of
semiconductor, (P stands for positive hole) since it is the positive hole that is responsible for
conduction.
Silicon atom Mobile electron Positive hole
(no electron)
As B
21. Lyophilic sols: Lyophilic sols are those sols in which the particles of dispersed phase have great
affinity for the dispersion medium, e.g., sols of gum, gelatine, starch, etc.
Lyophobic sols: In this type of sols the particles of dispersed phase have little or no affinity for
the dispersion medium, e.g., gold sol, Fe (OH) 3 sol, As 2 O3 sol., etc.
Lyophobic sols easily coagulate on the addition of small amount of electrolyte because these are
not stable. The stability of Lyophobic sols is only due to the presence of charge on the colloidal
particles, on the other hand stability of lyophilic sol. is due to charge as well as solvation of
colloidal particles.
22. (i) The principle of froth floatation process is that sulphide ore particle are preferentially wetted by
pine oil, whereas the gangue particles are wetted by water.
(ii) Zone refining is based on the principle that the impurities are more soluble in (liquid state) than
in the solid state of the metal.
(iii) The principle of refining by liquation is that the impurities whose melting points are higher than
the metal are left behind on melting the impure metal. Hence pure metal separates out.
23. (i) 3Cl 2 + 6NaOH ¾¾® 5NaCl + NaClO3 + 3H2 O
(Hot & conc.)
D
(ii) 4H3 PO3 ¾¾® 3H3 PO4 + PH3
(iii) PtF6 + Xe ¾¾® Xe + [PtF6 ] -
OR
(i) Ca 3 P2 (s) + 6H2 O(l) ¾¾® 2PH3 + 3Ca (OH) 2
(ii) Cu 2+ (aq) + 4NH3 (aq) r [Cu(NH3 ) 4 ] 2+ (aq)
(blue) (excess) (deep blue)
24. (a) The ion, atom or molecule bound to the central atom/ion in the coordination entity is called
ligand. A ligand should have lone pair of electrons in their valence orbital which can be donated
to central metal atom/ion.
·· ··
Bidentate ligand: H2 N ¾ CH2 ¾ CH2 ¾ N H2
(Ethylene diamine)
(b)
3d 4s 4p
Orbital of
Ni2+ ion
dsp 2 hybridised
orbitals of Ni2+
dsp 2 hybrid
[Ni(CN)4 ]2-
(Low spin complex)
Four pairs of
electrons from
4CN- group.
Orbital of
Ni (O)
3d 4s 4p
sp 3 hybridised
orbitals of Ni
3d sp 3 hybrid
Ni(CO) 4
(Low spin complex)
3d Four pairs of electrons from
four CO molecules
Structure: Tetrahedral
Magnetic behaviour: Diamagnetic due to the absence of unpaired electrons.
+
25. (i) Pyridinium chlorochromate (C5 H5 N HCrO3 Cl - ) or Cu/573 K
(ii) LiAlH4 / ether (iii) Br2 / H2 O
26. (i) In aniline due to resonance the lone pair of electrons on the nitrogen atom are delocalized over
the benzene ring. As a result, the electron density on the nitrogen decreases. On the other hand,
in methyl amine +I effect of CH3 increases the electron density on the nitrogen atom. Therefore
aniline is a weaker base than methyl amine and hence its pK b value is higher than that of
methyl amine.
CH3 ¾ NH2 + H2 O r CH3 N H3 + OH–
+
(ii)
Due to alkaline nature of solution of methylamine precipitation of Fe(OH) 3 occurs.
FeCl 3 + 3OH– ¾¾® Fe (OH) 3 ¯ + 3Cl -
Ferric hydroxide
(Brown ppt)
(iii) Aniline being a Lewis base, reacts with lewis acid AlCl 3 to form a salt. Due to this N atom of
aniline acquires positive charge and hence acts as a strong deactivation group for further
reaction.
27.
Polymer Monomer Structure of Monomer
(i) Buna-S Buta-1, 3-diene CH2 = CH ¾ CH = CH2
CH = CH2
and styrene ½
(b) (i) Chromite ore is fused with sodium carbonate in excess of air.
4FeCr2 O4 + 8Na 2 CO3 + 7O2 ¾® 8Na 2 CrO4 + 2Fe 2 O3 + 8CO2
Chromite ore Sod. chromate
(ii) Pyrolusite ore (MnO2 ) is fused with KOH in the presence of O2 or oxidising agent
such as KNO3 .
2MnO2 + 4KOH + O2 ¾® 2K 2 MnO4 + 2H2 O
Pyrolusite ore Potassium maganate
(b) (i) Cannizzaro reaction: Aldehydes which do not have an a-hydrogen, undergo self
oxidation and reduction (disproportionation) reaction on treatment with concentrated
alkali. In this reaction one molecule of the aldehyde is reduced to alcohol while another is
oxidised to carboxylic acid salt.
conc. KOH
2HCHO ¾¾¾¾¾® CH3 ¾ OH + HCOO- K +
Formaldehyde Methyl alcohol Potasium formate
(ii) Cross aldol condensation: When aldol condensation is carried out between two different
aldehydes and/or ketones, it is called cross aldol condensation.
O O
½½ OH – ½½
¾ CHO + ¾ C ¾ CH3 ¾¾¾® ¾ CH = CH ¾ C ¾
293 K
OR
(a) (i) This is due to steric and electronic reasons. Sterically, the presence of two relatively large
substituents in ketones hinders the approach of nucleophile to carbonyl carbon than in
aldehydes having only one such substituent. Electronically two alkyl groups reduce the
positivity of the carbonyl carbon more effectively in ketones than in aldehydes.
(ii) This is due to intermolecular hydrogen bonding in carboxylic acids.
(iii) Due to greater electronegativity of oxygen than carbon the C atom of the C = O bond
acquires a partial positive charge in aldehydes and ketones and hence readily undergo
nucleophilic addition reactions.
(b) (i) Acetaldehyde reacts with NaOI (I 2 / NaOH) to form yellow ppt of iodoform while
benzaldehyde does not give this test.
CH3 ¾ CHO + 3NaOI ¾® HCOO- Na + + CHI 3 + 2NaOH
Iodoform
(yellow ppt)
CHO
½
NaOI
¾¾¾¾® No reaction
(ii) Propanone give orange-red ppt with 2, 4-DNP reagent and yellow ppt of iodoform with
sodium hypoiodite, whereas 1-propanol does not give these tests.
CH3 ¾ COCH3 + 3NaOI ¾® CHI 3 + CH3 ¾ COO- Na + + 2NaOH
Iodoform
yellow ppt.
NaOI
CH3 ¾ CH2 ¾ CH2 ¾ OH ¾ ¾¾® No yellow ppt. of iodoform
OR
Osmotic pressure ( p) is defined as the extra pressure that must be applied to the solution side in
order to prevent the flow of solvent molecules into it through a semipermeable membrane.
n
p = B RT = CRT
V
where V is the volume of solution in litres containing n B moles of the solute.
If WB grams of the solute whose molecular mass M B is present in the solution then
W RT
p= B
M B RT
W RT
MB = B
pV
Thus, knowing WB , T , p and V molecular mass of the solute, M B can be calculated.
10. k = 0.0248 S cm -1 , M = 0.2 mol L-1
Substituting the values
k ´ 1000 0.0248 ´ 1000
Lm = =
M 0.2
L m = 1248 cm 2 mol -1
11. Zn Zn 2+ (conc.) Ag + (conc) Ag
(i) Zn electrode is negatively charged.
(ii) At anode Zn ¾¾® Zn 2+ + 2e -
At cathode 2Ag + + e - ¾® 2Ag
(iii) Current carriers of cell are
* electrons in external wire.
* Zn 2+ ions in anodic half cell.
* Ag + ions in cathodic half cell.
* Ions of salt bridge, i.e., K + and Cl - .
14. (i) C 6 H5 N2 Cl + KI ¾® C 6 H5 I + KCl + N2
Iodobenzene
H H CCl 4 H H
(ii) C=C + Br2 ¾¾¾® C¾ C
H H H ½ ½ H
Br Br
1, 2-Dibromoethane
15. (i) In haloarenes C—X bond acquires a partial double bond character due to resonance. As a result
the bond cleavage in haloarenes is difficult than haloalkanes and therefore, they are less reactive
towards nucleophilic substitution reaction.
X +X +X + X X
| |
18 | Xam idea Chemistry–XII
Cl
(ii) Or
Cl
I II
Compound (I) reacts faster in SN1 reaction as it is a 2° alkyl halide.
28. (a) Consider the first order reaction
R ¾¾® P
d [R ]
Rate = - = K [R ]
dt
d [R ]
or = - K dt
[R ]
Integrating both the sides we get
ln [ R ] = - Kt + C …(i)
when t = 0, R = [ R ] 0 where [ R ] 0 is the initial concentration of the reactant.
Therefore equation (i) can be written as
ln [ R ] 0 = - K ´ 0 + C
ln [ R ] 0 = C
Substituting the value of C in equation (i)
ln [ R ] = - Kt + ln [ R ] 0
Kt = ln [ R ] 0 - ln [ R ]
ln [ R ] 0
Kt =
[R ]
[R ]0 2.303 [R ]0
Kt = 2.303 log Þ t= log
[R ] K [R ]
[R ]0
when t = t 1/ 2 [R ] =
2
2.303 [R ]0
\ t 1/ 2 = log
K [R ]0
2
2.303 2.303
t 1/ 2 = log 2 = ´ 0.3010
K K
0.693
\ t 1/ 2 =
K
(b) 2NH3 ¾¾® N2 + 3H2
For a zero order reaction
Rate = K [ NH3 ] 0
Rate = K = 2.5 ´ 10 -4
1 d [ NH3 ] d [ N2 ] 1 d [ H2 ]
Rate = - = =
2 dt dt 3 dt
d [ N2 ] -4 -1 -1
\ = 2.5 ´ 10 mol L S
dt
d [ H2 ] 3d [ N2 ]
= = 3 ´ 2.5 ´ 10 -4 mol L-1 S -1
dt dt
d [ H2 ]
= 7.5 ´ 10 -4 mol L-1 S -1
dt
Examination Papers | 19
OR
(a) Rate of reaction depends on
(i) Concentration (ii) Temperature
(iii) Nature of reactant (iv) Pressure of the gaseous reactant
(v) Surface area (vi) Catalyst
(b) t 1/ 2 = 5730 years
0.693 0.693
\ K= = = 1.209 ´ 10 -4 year -1
t 1/ 2 5730
2.303 [R ]0 2.303 100
t= log = log
K [ R ] 1.2 ´ 10 -4 80
2.303 ´ 10 4 2.303 ´ 10 4
t= (log 10 - log 8) = (1 - 3 log 2)
1.2 1.2
2.303 2.303 ´ 0.097 ´ 10 4
t= ´ 10 4 (1 - 3 ´ 0.3010) =
1.2 1.209
t = 1847.7 years
K 2 Cr2 O7 /H 2 SO4 (O)
29. (a) (i) CH3 ¾ CH2 ¾ OH ¾¾¾¾¾¾¾® CH3 ¾ CHO ¾® CH3 ¾ COOH
Ethyl alcohol (O) Acetic acid
O
½½ O
Ca (OH) 2 O ¾ C ¾ CH3 Dry distill ½½
¾¾¾® Ca ¾¾¾¾¾® CH3 ¾ C ¾ CH3
O ¾ C ¾ CH3 Acetone
½½
O
Calcium acetate
O
½½
C ¾ CH3
O ½
½½ anhyd. AlCl 3
(ii) + CH3 ¾ C ¾ Cl ¾¾¾¾¾¾¾¾® + HCl
Acetyl chloride Friedel craft acylation
Benzene Acetophenone
O O O
½½ ½½ ½½
C ¾ OH C ¾ Cl C¾ H
½ ½ ½
PCl5 + H2
(iii) ¾¾¾® ¾¾¾¾®
Pd/BaSO4
(b) (i) Decarboxylation: Carboxylic acids lose CO2 to form hydrocarbons when their sodium salts are
heated with soda lime (NaOH and CaO in the ratio 3: 1).
NaOH and CaO
R ¾ COONa ¾¾¾¾¾¾¾® R ¾ H + Na 2 CO3
D
COONa
½
NaOH /CaO
¾¾¾¾® + Na 2 CO3
D
O
½½ Iodoform
CH3 ¾ C ¾ CH2 ¾ CH2 ¾ CH3 + 3I 2 + 4NaOH ¾¾¾¾¾® CHI 3
reaction Iodoform
Yellow ppt.
- +
+ CH3 ¾ CH2 ¾ CH2 ¾ CO O Na + 3NaI + 3H2 O
O
½½ : K 2 Cr2 O7 /H 2 SO4
CH3 ¾ C ¾ CH2 ¾ CH2 ¾ CH3 ¾¾¾¾¾® CH3 ¾ COOH + CH3 ¾ CH2 ¾ COOH
: (O) Ethanoic acid Propanoic acid
(b) (i) This is because dichloroethanoic acid is a stronger acid than monochloroethanoic acid.
(ii) This is because methyl group due to its positive inductive effect destabilize the acetate
anion by intensifying the negative charge.
k ´ 1000
2. lm =
c
where, L m = Molar conductivity
k = Conductivity
c = Molar concentration
3. Chemisorption
1
10. k = ´ cell constant
R
k = 0.146 ´ 10 -3 S cm -1 , R = 1500 ohm
1
0.146 ´ 10 -3 = ´ cell constant
1500
cell constant = 0.146 ´ 10 -3 ´ 1500 = 219 ´ 10 -3 = 0.219 cm -1
19. (i) This is because alkali metal ions have larger size which cannot fit into interstitial sites.
(ii) As the number of ions decreases as a result of Schottky defect, the mass decreases whereas the
volume remains the same.
(iii) This is due to additional electron or creation of hole on dopping with impurity.
Creation of hole causes p-type semiconductor and creation of electron causes n-type semiconductor.
OR
(i) Ferromagnetism: Ferromagnetic substances are those substance which are strongly attracted
by external magnetic fielding, e.g., (iron, cobalt, nickle and CrO2 , etc.] Ferromagnetism arises
due to spontaneous alignment of magnetic moments in the same direction.
(ii) Paramagnetism: Paramagnetic substances are those substances which are weakly attracted by
magnetic field. It is due to the presence of one or more unpaired electrons, e.g.,O2 , Fe 3+ , Cr 3+ ,
etc.
(iii) Ferrimagnetism: Ferrimagnetism is observed when the magnetic moments of the domains in
the substance are aligned in parallel and antiparallel directions in unequal number resulting in
some net magnetic moment, e.g., Fe 3 O4 (magnetite) and ferrites like MgFe 2 O4 , etc.
21. (i) Zone refining is based on the principle that the impurities are more soluble in the melt in than
solid state of metal.
(ii) Vapour phase refining.
In this, metal is converted into its volatile compound and collected elsewhere. It is the
decomposed to give pure metal. So, the two requirements are:
(a) the metal should form a volatile compound with an available reagent.
(b) the volatile compound should be easily decomposable, so that the recovery is easy.
(iii) In electrolytic refining impure metal is made to act as anode. A strip of the same metal in pure
form is used as cathode. They are put in a suitable electrolytic bath containing soluble salt of the
same metal. When electric current is passed, impure metal forms metal ions which are
discharged at cathode forming pure metal.
Anode: M ¾® M n + + ne -
Cathode: M n + + ne - ¾® M
22. (i) The positively charged colloidal particles of Fe(OH) 3 get coagulated by the oppositely charged
Cl - ions provided by KCl.
(ii) On passing direct current, colloidal particles move towards the oppositely charged electrode
where they lose their charge and get coagulated.
(iii) Scattering of light by the colloidal particles takes place and the path of light becomes visible
(Tyndall effect).
CBSE EXAMINATION PAPERS
ALL INDIA—2008
Time allowed: 3 hours Maximum marks: 70
General Instructions:
(i) All questions are compulsory.
(ii) Question nos. 1 to 8 are very short answer questions and carry 1 mark each.
(iii) Question nos. 9 to 18 are short answer questions and carry 2 marks each.
(iv) Question nos. 19 to 27 are also short answer questions and carry 3 marks each.
(v) Question nos. 28 to 30 are long answer questions and carry 5 marks each.
(vi) Use log tables if necessary, use of calculators is not allowed.
CH2 Cl
(ii)
15. Alcohols react both as nucleophiles as well as electrophiles. Write one reaction of each type and
describe its mechanism.
16. How would you carry out the following conversions?
(i) Ethyl magnesium chloride to propan-1-ol
(ii) Benzyl chloride to benzyl alcohol
H 2 NCONHNH 2
(i) CH3 CHO ¾¾¾¾¾¾® .......... (?)
(i) O3
(ii) (?) ........... ¾¾¾¾¾¾® 2 O
(ii) Zn - H 2 O
26 | Xam idea Chemistry–XII
.................. (?)
(iii) CH2 ¾¾¾¾¾® ¾ CHO
OR
(a) State tests to distinguish between the following pairs of compounds :
(i) Propanal and propanone
(ii) Phenol and benzoic acid
(b) How will you bring about the following conversions :
(i) Propanone to propene
(ii) Benzaldehyde to benzophenone
(iii) Ethanol to 3-hydroxybutanal
(a) Define conductivity and molar conductivity for the solution of an electrolyte. How do they vary
when the concentration of electrolyte in the solution increases?
(b) Three conductivity cells A, B and C containing solutions of zinc sulphate, silver nitrate and
copper sulphate respectively are connected in series. A steady current of 1.5 amperes is passed
through them until 1.45 g of silver is deposited at the cathode of cell B. How long did the
current flow? What mass of copper and what mass of zinc got deposited in their respective
cells?
(Atomic mass : Zn = 65.4 u, Ag = 108 u, Cu = 63.5 u)
SOLUTIONS
CBSE (All India) SET–I
1. The difference of energy between conduction band and valence band is called forbidden zone and
for insulator its value is averaging between 3–6 eV.
2. This can be done
(i) by adding an electrolyte.
(ii) by adding a suitable solvent.
3. Cl 2 exhibits - 1, + 1, + 3, + 5, + 7 oxidation states in its compounds.
4. Lower members aldehydes are able to form intermolecular hydrogen bonds with water molecules.
Hence, they are easily miscible with water.
5. Due to the presence of a lone pair of electrons on nitrogen atom.
6. Carbohydrates that yield two monosaccharide units, on hydrolysis are called disaccharides, e.g.,
sucrose.
7. The process of formation of polymers from respective monomers is called polymerisation.
O2 , 350K -570 K
1000-2000 atm
nCH2 = CH2 ¾¾¾¾¾¾¾® ¾
( CH2 ¾ CH2 ¾
)n
Ethene Polymerisation Polyethene (LDP)
(monomer) (polymer)
8. Chemotherapy: It is the branch of chemistry which deals with the treatment of diseases using
suitable chemicals.
9. Osmotic pressure ( p) may be defined as the extra pressure that must be applied to the solution to
prevent the flow of solvent molecules into it through a semipermeable membrane.
n
p = B RT = CRT
V
WB . R. T
p=
M B .V
where V is the volume of solution in litre containing n B moles of solute of molecular mass M B .
Thus knowing p, WB , T and V molecular mass of the solute M B can be calculated.
The osmotic pressure method has the advantage over rise in boiling point or fall in freezing point
for determining molar masses of macromolecules because
(i) Osmotic pressure is measured at the room temperature and the molarity of solution is used
instead of molality.
(ii) Compared to other colligative properties, its magnitude is large even for very dilute solutions.
OR
For a solution of volatile liquids Raoult’s law, is given as
P = PA + PB
If solute (component B) is non-volatile then
P = PA = PAo x A
P = PAo (1 - x B ) (Q x A + x B = 1)
P= PAo - PAo x B
PAo x B = PAo - P
Examination Papers | 29
PAo - P
= xB
PAo
Thus, relative lowering of vapour pressure is equal to the mole fraction of non-volatile solute.
10. K = 0.0248 S cm -1
M = 0.2 mol L-1
K ´ 1000 0.0248 ´ 1000
lm = =
M 0.2
l m = 124 S cm 2 mol -1
11. (i) It is due to
(a) Intermolecular hydrogen bonding in HF.
(b) Higher H—F bond dissociation enthalpy than H—Cl.
(ii) As P—P single bond (213 kJ mol -1 ) in P4 is much weaker than N º N triple bond
(941.4 kJ mol -1 ) in N2 .
12. On the basis of electrochemical series the standard electrode potential shows the following order
E° Mn 2 + /Mn < E° Cr 2 + /Cr < E° Fe2 + /Fe < E° Co 2 + /Co
Therefore, Co 2+ gets easily reduced to metallic cobalt while it is difficult to reduce Mn 2+ . Hence
Mn 2+ will be most stable and the increasing stability order will be
Co 2+ < Fe 2+ < Cr 2+ < Mn 2+
13. When bromine reacts with propyne, the reddish brown colour of bromine is discharged as long as
propyne is present in excess.
Br Br Br
CCl 4 ½ + Br2 ½ ½
CH3 ¾ C º CH + Br2 ¾® CH3 ¾ C = C ¾ H ¾¾® CH3 ¾ C ¾ C ¾ H
Propyne ½ ½ ½
Br Br Br
1, 1, 2, 2, Tetra Bromo propane
(colourless)
This is due to the formation of 1, 1, 2, 2-tetrabromo propane which is colourless.
CH3
½ ¾ CH2 ¾ Cl
14. (i) CH3 ¾ C ¾ CH2 ¾ Br (ii)
½
CH3 Phenyl chloromethane
1-Bromo-2, 2-dimethyl propane
15. Alcohols as nucleophile:
The bond between O—H is broken when an alcohol reacts as a nucleophile.
H+
R ¾ COOH + R¢¾ OH r R ¾ COOR¢ + H2 O
Carboxylic acid Alcohol Ester
30 | Xam idea Chemistry–XII
Mechanism:
··
·· + ·
·· OH
·
O OH R¢ ¾ O ¾ H
·· H+ ·· ½ +
r r
··
R¾ C R¾ C R ¾ C ¾ O· ¾ R¢
·
·· OH ½ ½
O¾H
·· · OH H
···
Tetrahedral intermediate
··
·· + Proton transfer ·
OH
·
O ·· O¾H
- H+ ·· -H2O
½
R¾ C r R¾ C r R ¾ C ¾ O ¾ R¢
·· ·· ½
O ¾ R¢ O ¾ R¢ +
·· ·· ·
Ester · O¾ H
½
H
Tetrahedral intermediate
Alcohols as electrophile:
The bond between C—O is broken when alcohols react as electrophiles.
R ¾ CH2 ¾ O ¾ H + HCl ¾¾® R ¾ CH2 ¾ Cl + H2 O
Alcohol
Mechanism
·· +
R ¾ CH2 ¾ O ¾ H + H+ ¾¾® R ¾ CH2 ¾ O H2
·· ··
- +
Cl + CH2 ¾ O H2 ¾¾® Cl ¾ CH2 + H2 O
½ ·· ½
R R
é OMgCl ù
O
ê ½ ú
½½ d- d+ ê ú
16. (i) H ¾ C ¾ H + CH3 ¾ CH2 Mg Cl ¾¾® ê H ¾ C ¾ H ú
Formaldehyde Ethyl magnesium
chloride ê ½ ú
ê CH2 ¾ CH3 úû
ë
H2O OH
¾¾¾® CH3 ¾ CH2 ¾ CH2 ¾ OH + Mg
Propan -1-ol Cl
CH2 ¾ Cl CH2 ¾ OH
½ ½
D
(ii) + KOH (aq) ¾¾¾® + KCl
Non-biodegradable detergents: Detergents having branched hydrocarbon chains are not easily
degraded by the micro-organism and hence are called non-biodegradable detergents, e.g.,
sodium-4-(1, 3, 5, 7-tetramethyl octyl) benzenesulphonate.
CH3 CH3
½ ½ +
CH3 ¾ ( CH ¾ CH2 ¾ ) 3 ¾ CH ¾ ¾ SO-3 Na
Non-biodegradable detergents accumulate in rivers and waterways thereby causing water pollution.
19. d = 8.55 g / cm 3 , M = 93 g / mol
For bcc, z = 2, a = ? N A = 6.02 ´ 10 23
z´M
d=
a3 ´ NA
Substituting the values
2 ´ 93
8.55 =
a ´ 6.02 ´ 10 23
3
2 ´ 93
a3 =
8.55 ´ 6.02 ´ 10 23
1/ 3
æ 930 ö
a=ç ÷ 10 -8
è 8.55 ´ 3.01 ø
1/ 3
æ 930 ö
Let x =ç ÷
è 8.55 ´ 3.01 ø
1/ 3
æ 930 ö
\ log x = log ç ÷
è 8.55 ´ 3.01 ø
1
= (log 930 - log 8.55 - log 3.01)
3
1
= ( 2.9685 - 0.9320 - 0.4786)
3
1
log x = (1.5579) = 0.5193
3
x = Antilog ( 0.5193)
x = 3.306
\ a = 3.306 ´ 10 -8 cm
32 | Xam idea Chemistry–XII
3
Now r= a
4
3 1.732 ´ 3.306 ´ 10 -8
\ r= ´ 3.306 ´ 10 -8 =
4 4
r = 1.4315 ´ 10 cm = 143.15 ´ 10 - 10 cm
-8
r = 143.15 pm
OR
(a) n-type semiconductor: When a silicon or germanium crystal is doped with group 15 element
like P or As, the dopant atom forms four covalent bonds like a Si or Ge atom but the fifth
electron, not used in bonding, becomes delocalised and contribute its share towards electrical
conduction. Thus silicon or germanium doped with P or As is called n-type semiconductor, n
indicative of negative, since it is the electron that conducts electricity.
p-type semiconductor: When silicon or germanium is doped with group 13 element like B or
Al, the dopant has only with three, valence electrons. An electron vacancy or a hole is created
at the place of the missing fourth electron. Here, this hole moves through the crystal like a
positive charge giving rise to electrical conductivity. Thus Si or Ge doped with B or Al is
called p type of semiconductor, (P stands for positive hole) since it is the positive hole that is
responsible for conduction.
(b) F-centres: Electrons trapped in anion vacancies are called F-centres. They impart characteristic
colour to the compound and increase electrical conductivity.
(c) Ferromagnetism: Ferromagnetic substances are those substances which are strongly attracted
by external magnetic field, e.g., (iron, cobalt, nickle and CrO2 etc.] Ferromagnetism arises due
to spontaneous alignment of magnetic moments in the same direction.
also n=2
DG ° = - nFE° cell
DG° = - 2 ´ 96500 ´ 1.10
DG° = 2.123 ´ 105 J
22. (i) Scattering of light by the colloidal particles takes place and the path of light becomes visible
(Tyndall effect).
(ii) The positively charged colloidal particles of Fe(OH) 3 get coagulated by the oppositely charged
Cl - ions provided by NaCl.
(iii) On passing direct current, colloidal particles move towards the oppositely charged electrode
where they lose their charge and get coagulated.
23. (i) Electrolytic reduction of Al 2 O 3 :
Cathode: Al 3+ (melt) + 3e - ¾® Al
Anode: C(s) + O2 - (melt) ¾® CO(g) + 2e -
C(s) + 2O2 - (melt) ¾® CO2 (g) + 4e -
(ii) Isolation of zinc from zinc blende:
D
Roasting: 2 ZnS + 3O2 ¾¾® 2 ZnO + 2 SO2
Zinc blende
1673 K
Reduction: ZnO + C ¾ ¾ ¾
¾® Zn + CO
(iii) Mond’s process for refining nickel:
330-350 K
Ni + 4CO ¾¾¾¾® Ni(CO) 4
450-470 K
Ni(CO) 4 ¾¾¾¾¾® Ni + 4CO
24.
Characteristics Lanthanoids Actinoids
1-14 0 -1 1-14
(i) Electronic configuration [Xe] 4f 5d 2
6s [Rn] 5f 6d 0 -17 s2
(ii) Oxidation states Besides + 3 O.S. lanthanoids Besides +3 O.S. actinoids show
show +2 and +3 O.S. only in a higher O.S. of +4, +5, +6, +7
few cases. also because of smaller energy
gap between 5f , 6d and 7s
subshell.
(iii) General chemical reactivity of These are less reactive metals These are highly reactive
elements metals.
Lesser tendency towards Greater tendency towards
complex formation. complex formation.
Do not form oxocation Form oxocation
Compounds are less basic. Compounds are more basic.
34 | Xam idea Chemistry–XII
O
½½ - H2O
H2 N ¾ CH2 ¾ C ¾ OH + H NH ¾ CH ¾ COOH ¾¾¾®
½
CH3
O
½½
H2 NCH2 ¾ C ¾ NH ¾ CH ¾ COOH
½
CH3
Peptide linkage
(Gly -Ala)
dx
28. (a) Rate = = K [A ] [B ]2
dt
If concentration of both A and B are doubled, then
Rate = K [ 2A ] [ 2B ] 2
= 8K [ A ] [ B ] 2
i.e., the rate of reaction becomes 8 times.
K2
(b) K 2 = 4K1 i.e., =4
K1
T1 = 300 K T2 = 320 K
K2 E a æ T2 - T1 ö
log = ç ÷
K1 2.303 R è T1T2 ø
Ea æ 320 - 300 ö
log 4 = ç ÷
2.303 ´ 8.314 è 300 ´ 320 ø
Ea æ 20 ö
2 log 2 = ç ÷
19.147 è 300 ´ 320 ø
2 ´ 0.3010 ´ 19.147 ´ 300 ´ 320
Ea = = 55327 J
20
E a = 55.327 kJ
OR
(a) Rate of reaction depends on
(i) Concentration
(ii) Temperature
(iii) Nature of reactant
(iv) Pressure of the gaseous reactant
(v) Surface area
(vi) Catalyst
(b) t 1/ 2 = 5730 years
0.693 0.693
\ K= = = 1.209 ´ 10 -4 year -1
t 1/ 2 5730
2.303 [R ]0 2.303 100
t= log = log
K [ R ] 1.2 ´ 10 - 4 80
36 | Xam idea Chemistry–XII
2.303 ´ 10 4 2.303 ´ 10 4
t= (log 10 - log 8) = (1 - 3 log 2)
1.2 1.2
2.303 2.303 ´ 0.097 ´ 10 4
t= ´ 10 4 (1 - 3 ´ 0.3010) =
1.2 1.209
t = 1847.7 years
29. (a) (i) Due to stronger inert pair effect Bi (V) gets readily reduced to Bi (III) therefore, Bi (V) is a
stronger oxidising agent than Sb (V).
(ii) Xe has least ionization enthalpy among noble gases and hence it readily forms chemical
compounds particularly with O2 and F2 .
O O
½½ ½½
(b) (i) S S
O
O O
OH OH
H2 S 2 O7 (Pyrosulphuric acid) F
(ii) BrF3 b. p. = 3
sp 3 d 5e Br F
hybridisation l. p. = 2 bent T
shaped
F
F
(ii) Decarboxylation
R ¾ COOH + NaOH ¾¾® R ¾ COONa + H2 O
Sodium carboxylate
NaOH /CaO
R ¾ COONa ¾¾¾¾® R¾ H + Na 2 CO3
D Hydrocarbon
O O
CH3 ½½ CH3 ½½
(b) (i) C = O + H2 N NH ¾ C ¾ NH2 ¾
¾® C = NNH ¾ C ¾ NH2 + H2 O
H Semi carbazide H Ethanal semicarbazone
Ethanal
O3
(ii) ¾¾¾® 2 O
Zn /H 2 O
(i) BH 3 /THF
(iii) CH2 ¾¾¾¾¾¾® —CHO
(ii) H 2 O2 / OH
(iii) PCC
OR
(a) (i) Propanone on treatment with I 2 / NaOH (NaOI) undergoes iodoform reaction to give yellow
ppt of iodoform but propanal does not.
CH3 COCH3 + 3NaOI ¾® CHI 3 ¯ + CH3 ¾ COONa + 2NaOH
Iodoform
(Yellow ppt)
CH3 ¾ CH2 ¾ CHO ¾¾¾¾® No yellow ppt. of Iodoform
Propanal
Tollen’s test: Propanal being an aldehyde reduces Tollen’s reagent to silver mirror but
propanone being a ketone does not.
CH3 ¾ CH2 ¾ CHO + 2 [Ag(NH3 ) 2 ] + + 3OH ¾¾® CH3 ¾ CH2 ¾ COO-
Propanal Tollen’s reagent
+ 2Ag ¯ + 4NH3 + 2H2 O
Silver mirror
(ii) FeCl 3 test: Phenol gives a violet colouration with neutral FeCl 3 solution while benzoic
acid gives buff coloured ppt.
6 C 6 H5 OH + FeCl 3 ¾¾® [Fe(OC 6 H5 ) 6 ] -3 + 3H+ + 3HCl
Violet complex
NaHCO 3 test: Benzoic acid being a stronger acid than phenol decomposes NaHCO3 to evolve
CO2 but phenol does not.
- +
C 6 H5 ¾ COOH + NaHCO3 ¾¾® C 6 H5 ¾ CO O Na + H2 O + CO2
Benzoic acid Sodium benzoate
O OH
½½ LiAlH 4 ½ conc. H 2 SO4
(b) (i) CH3 ¾ C ¾ CH3 ¾¾¾® CH3 ¾ CH ¾ CH3 ¾¾¾¾¾® CH3 ¾ CH = CH2
Propanone 443 K Propene
38 | Xam Idea Chemistry–XII
O
CHO COOH COCl
+ C
KMnO4 /OH PCl5
(ii) (O) anhyd. AlCl3
OH
PCC ½ NaOH (dil.)
(iii) CH3 ¾ CH2 ¾ OH ¾¾¾® CH3 ¾ CHO ¾¾¾¾® CH3 ¾ CH ¾ CH2 ¾ CHO
Ethanol Acetaldehyde 3-Hydroxybutanal
Cu 2+ + 2e - ¾¾® Cu
2 ´ 96500 C deposit Cu = 63.5 g
63.5
\ 1295.6 C deposit Cu = ´ 1295.6 = 0.426 g
2 ´ 96500
Zn 2+ + 2e - ¾¾® Zn
2 ´ 96500 C deposit Zn = 65.3 g
65.3
\ 1295.6 C deposit Zn = ´ 1295.6 = 0.438 g
2 ´ 96500
CBSE (All India) SET–III
1. Boron or Aluminium.
10. A reaction which is of higher order but follows the kinetics of first order under special conditions
is called a pseudo first order reaction.
Example, Acid hydrolysis of ethyl acetate.
H+
CH3 ¾ COOC 2 H5 + H2 O ¾¾® CH3 ¾ COOH + C 2 H5 ¾ OH
Here, the rate law is given by expression
Rate = K [ CH3 ¾ COOC 2 H5 ]
The concentration of H2 O is so large that it hardly undergoes any change during the reaction,
therefore, it does not appear in the rate law.
12. (i) This is because Mn 2+ is more stable as it has exactly half filled configuration 3d 5 4s 0 .
(ii) Cu 2+ (aq) is much more stable than Cu + (aq). This is because, although second ionization
enthalpy of copper is large but for Cu 2+ (aq) is much more negative than that of Cu + (aq) and
therefore, it more than compensates for the second ionisation enthalpy of copper. Therefore,
Cu + ion aqueous solution undergoes disproportionation.
2Cu + (aq) ¾® Cu 2+ (aq) + Cu(s)
18. Artificial sweetening agents: These are the substances which are non-nutritive in nature and used
as substitutes for sugar in foods and beverages.
Examples:
Aspartame: Aspartame is 100 times as sweet as cane sugar. Its use is limited to cold foods and
soft drinks because it is unstable at cooking temperature.
Saccharin: It is about 550 times as sweet as cane sugar. Its use is of great value to diabetic
persons and people who need to control intake of calories.
21. K = 60 s -1
2.303 [R ]0
t= log
K [R ]
2.303 [ R ] 0 2.303
t= log = log 10 = 0.038 ´ 1
60 [R ]0 60
10
t = 0.038 s
24. (i) As there is very little energy difference between 4s and 3d orbitals, electrons from both energy
levels can be used for chemical bond formation. Therefore all elements except Sc and Zn, of the
first transition series show a number of oxidation states as shown in table.
42 | Xam idea Chemistry–XII
Oxidation states of the first series transition elements (the most common ones are in bold letter)
Sc Ti V Cr Mn Fe Co Ni Cu Zn
+2 +2 +2 +2 +2 +2 +2 +1
+3 +3 +3 +3 +3 +3 +3 +3 +2 +2
+4 +4 +4 +4 +4 +4 +4
+5 +5 +5
+6 +6 +6
+7
(ii) Atomic radii of the first transition series decreases from Sc to Cr, then remains almost constant
till Ni and then increases from Cu to Zn.
The reason of this variation in atomic radii has been attributed to the increase in nuclear charge
in the beginning of the series. But as the electrons continue to be filled in d-orbitals, they screen
the outer 4s electrons from the influence of nuclear charge. When the increased nuclear charge
and the increased screening effect balance each other in the middle of transition series, the
atomic radii becomes almost constant (Mn to Fe). Towards the end of the series, the repulsive
interaction between electrons in d orbitals become very dominant. As a result there is an
expansion of the electron cloud; consequently, the atomic size increases.
(iii) Except Zn 2+ , all other divalent gaseous ions of the first series of the transition elements contain
unpaired electrons in their 3d subshell and are therefore paramagnetic in nature.
The magnetic moment (m) of the elements of the first transition series can be calculated with the
unpaired electrons ( n) by the spin-only formula
m = n ( n + 2) B. M.
Zn 2+ 3d10 4s0 0 0 ( 0 + 3) = 0
CBSE EXAMINATION PAPERS
DELHI–2009
Time allowed : 3 hours Maximum marks : 70
General Instructions:
(i) All questions are compulsory.
(ii) Question nos. 1 to 8 are very short answer questions and carry 1 mark each.
(iii) Question nos. 9 to 18 are short answer questions and carry 2 marks each.
(iv) Question nos. 19 to 27 are also short answer questions and carry 3 marks each.
(v) Question nos. 28 to 30 are long answer questions and carry 5 marks each.
(vi) Use log tables if necessary, use of calculators is not allowed.
13. Differentiate between molality and molarity of a solution. What is the effect of change in temperature
of a solution on its molality and molarity? 2
14. Which ones in the following pairs of substances undergoes SN2 substitution reaction faster and why? 2
(ii) I or Cl
CH2OH
(ii) + HCl
OH
OR
(a) State the relationship amongst cell constant of a cell, resistance of the solution in the cell and
conductivity of the solution. How is molar conductivity of a solute related to conductivity of its
solution?
(b) A voltaic cell is set up at 25oC with the following half-cells:
Al | Al3+ (0.001 M) and Ni | Ni2+ (0.50 M)
Calculate the cell voltage [EoNi2+/Ni = – 0.25 V, EoAl/Al3+ = – 1.66 V]
29. (a) Complete the following chemical reaction equations: 5
(i) MnO–4( aq ) + C 2 O2–
4 ( aq ) + H +
( aq ) ¾¾®
2– 2+ +
(ii) Cr2 O7( aq ) + F ( aq ) + H ( aq ) ¾¾®
(b) Explain the following observations about the transition/inner transition elements:
(i) There is in general an increase in density of element from titanium (Z = 22) to copper (Z = 29).
(ii) There occurs much more frequent metal-metal bonding in compounds of heavy transition
elements (3rd series).
(iii) The members in the actinoid series exhibit a large number of oxidation states than the
corresponding members in the lanthanoid series.
OR
(a) Complete the following chemical equations for reactions:
(i) MnO4–(aq) + S2O32–(aq) + H2O(l) ¾¾®
(ii) CrO7–(aq) + H2S(g) + H+(aq) ¾¾®
OR
(a) How are the following obtained?
(i) Benzoic acid from ethyl benzene.
(ii) Benzaldehyde from toluene.
(b) Complete each synthesis by giving the missing material, reagent or products:
H2
(i) C6H5COCl Pd-BaSO4
................
O
C
(ii) + .............. Anhydrous AlCl3 CH3
O
C
+ .............. ..............
(iii)
OR
(a) Complete the following chemical reaction equations:
(i) CrO72–(aq) + H2S(g) + H+(aq) ¾¾®
(ii) MnO2(s) + KOH (aq) + O(2) ¾¾®
(b) Explain the following observations:
(i) Transition metals form compounds which are usually coloured.
(ii) Transition metals exhibit variable oxidation states.
(iii) The actinoids exhibit a greater range of oxidation states than the lanthanoids.
29. (a) What type of a cell is the lead storage battery? Write the anode and the cathode reactions and
the overall reaction occurring in a lead storage battery while operating.
(b) A voltaic cell is set up at 25°C with the half-cells Al | Al3+ (0.001 M) and Ni | Ni2+ (0.50 M).
Write the equation for the reaction that occurs when the cell generates an electric current and
determine the cell potential.
(Given: E oNi 2 + Ni
= –0.25V, E oAl 3+ Al
= –1.66V).
OR
(a) Express the relationship amongst cell constant, resistance of the solution in the cell and
conductivity of the solution. How is molar conductivity of a solute related to conductivity of its
solution.
(b) Calculate the equilibrium constant for the reaction.
Fe( s) + Cd 2 + ( aq) ® Fe 2 + (aq ) + Cd( s)
(Given: E oCd 2 + Cd
= – 0.40 V, E oFe 2 + Fe
= – 0.44 V).
27. What are the following substances? Give one example of each type.
(i) Antacid (ii) Nonionic detergents (iii) Antiseptics
28. (a) Complete the following chemical reaction equations:
(i) Cr2O 72- (aq) + I - (aq) + H + (aq) ¾¾®
OR
(a) Corrosion is essentially an electrochemical phenomenon. Explain the reactions occurring
during corrosion of iron kept in an open atmosphere.
(b) Calculate the equilibrium constant for the equilibrium reaction.
Fe( s) + Cd 2(+aq ) l Fe 2(+aq ) + Cd( s)
SOLUTIONS
13. Molality is the number of moles of solute per thousand grams of solvent whereas molarity is the
number of moles of solute dissolved in one litre of solution.
Molality is independent of temperature whereas molarity changes with change in temperature as
volume changes with temperature.
14. (i) —CH2Cl : It is primary halide therefore undergoes SN2 reaction faster.
(ii) : As iodine is a better leaving group because of its large size, it will
I be released at a faster rate in the presence of incoming nucleophile
HO HO
O
||
16. (i) The — C— NH — bond formed between two amino acid molecules with loss of water in a
polypeptide is called peptide linkage.
(ii) The linkage between two monosaccharides molecules through oxygen atom in a disaccharide
or polysaccharide is known as glycosidic linkage.
17. B group vitamins and vitamins C are soluble in water.
Name of Vitamins Sources Deficiency diseases
(i) Vitamin B12 Meat, fish, egg and curd Pernicious anaemia
(ii) Vitamin C Citrus fruits and amla Scurvy
18.
Polymer Monomer Structure
(i) Teflon Tetrafluoroethene F F
| |
F - C = C- F
(ii) Polyethene Ethene H H
| |
H - C = C- H
OR
O O
|| ||
n HO — C — CH2 — CH2 — C— OH + n H2 N — CH2 — CH2 — NH2
¯
é O O ù
ê || || ú
ê C— CH2 — CH2 — C — HN — CH2 — CH2 — NH ú + 2nH2 O
ê ú
ê ú
ë ûn
52 | Xam Idea Chemistry–XII
2 ´ 56 g mol -1
7.87g cm–3 =
(286.65 ´ 10 -3 cm) 3 ´ NA
2 ´ 56 g mol -1
NA =
(2.8665 ´ 10 -8 cm) 3 ´ 7.87 g cm -3
2 ´ 56 g mol -1
=
23.553 ´ 10 -24 cm 3 ´ 7.87 g cm -3
112 mol -1
= = 0.604 × 1024 mol–1
185.366 ´ 10 -24
= 6.024 × 1023 mol–1
W ´ R ´T
20. p = B
MB ´V
WB ´ R ´ T
MB =
p´ V
Here
WB = 100 mg = 100 × 100–3g
R = 0.0821 L atm K–1 mol–1
T = 25°C = (25 + 273) K = 298K
V = 10 mL = 10 × 10–3L
13.3
p = 13.3 mm Hg = atm
760
100 ´ 10 -3 g ´ 0.0821 L atm K -1 mol -1 ´ 298K
MB =
13.3
atm ´ 10 ´ 10 -3 L
760
100 ´ 10 -3 ´ 0.0821 ´ 298 ´ 760 g mol -1 18594 g mol -1
MB = =
13.3 ´ 10 ´ 10 -3 133
MB = 13980.45 g mol–1
21. For a first order reaction
2.303 [R] o
t = log
k [R]
Here
Examination Papers | 53
23. (i) NH3 is stronger base than PH3. This is because the lone pair of electrons on N atom in NH3 is
directed and not diffused as it is in PH3 due to larger size of phosphorus and hence more
available for donation.
(ii) Sulphur has a greater tendency for catenation than oxygen because S-S bond is stronger than
O – O bond due to less interelectronic repulsions.
(iii) Bond dissociation energy of F2 is less than Cl2 this is due to relatively large electron – electron
repulsion among the lone pairs in F2 molecule where they are much closer to each other than in
case of Cl2.
OR
–
O
–
–– + –O
+–
(i) H—O—N – HO—N –
O O
As a result of resonance, N–O bond length is average of single bond and double bond whereas
N–OH bond has purely single bond character. Therefore, N–O bond is shorter than N–OH
bond in HNO3.
(ii) S atom in SF4 is not sterically protected as it is surrounded by only four F atoms, so attack of
H2O molecules can take place easily and hence hydrolysis takes place easily. In contract, in
SF6, S is sterically protected by six F atoms. Therefore does not allow H2O molecules to attack
S atoms. As a result of this, SF6 does not undergo hydrolysis.
54 | Xam idea Chemistry–XII
(iii) In XeF2, Xe is sp3d hybridised having 2 bond pair and 3 lone pair of electrons. The presence of
3 lone pair of electrons in Xe F2 at equidistance to have minimum repulsion is responsible for
its linear structure.
24. Given complex is [Fe (en) 2 Cl 2 ]Cl
(i) Let the oxidation number of iron be x.
\ x + 2 ´ 0 + 2(–1) + 1( -1) = 0
Þ x =3
3d 4s 4p
R R
Step II: Hydrolysis
d+ d– d– d+ –+
C O + R — Mg — X C OMg — X
R
Adduct
+
(ii) CH3 — CH2 — OH ¾H¾
¾® CH2 CH2 + H2 O
D
Mechanism
Step I: Formation of protonated alcohols
H H H H H
+ Fast +
H— C— C — O — H + H H— C— C — O — H
H H H H
Ethyl alcohol Ethyl oxonium ion
Examination Papers | 55
Step II: Formation of carbocation: It is the slowest step and hence, the rate determining step.
H H H H H
+ Slow +
H— C — C — O — H H— C — C + H2O
H H H H
Ethyl oxonium ion Ethyl carbocation
Alkene H OH
Mechanism
Step I: Protonation of alkene to form carbocation by electrophilic attack of H3O+.
+
H2O + H H3O +
H H
+ +
—C
C— + H—O—H —C—C + H2O
l
+ +
—C—C + H2O —C—C—O—H
26. (i) Hoffman’s bromamide reaction: When a primary acidamide is heated with bromine in an
aqueous or ethanolic solution of sodium hydroxide, it gives a primary amine with one carbon
atom less. In this degradation reaction, migration of an alkyl or aryl group takes place from
carbonyl carbon of the amide to the nitrogen atom.
O
(ii) Gattermann reaction: Chlorine or bromine can be introduced in benzene ring by treating the
diazonium salt solution with corresponding halogen acid in the presence of copper powder.
Cl
+ – Cu / HCl
N2Cl + N2 + CuCl
Chlorobenzene
Br
Benzene diazonium
chloride Cu / HBr
+ N2 + CuCl
Bromobenzene
(iii) Coupling reaction: Diazonium salts react with aromatic amines in weakly acidic medium and
with phenols in weakly alkaline medium to form coloured compounds called azo dyes by
coupling at para position of amines or phenols. The mechanism is basically that of electrophilic
aromatic substitution where the diazonium ion is electrophile.
+ – H
+ –
N NCl + H— — NH 2 N N— — NH 2 + Cl + H 2O
(pH 4-5)
+ – –
OH –
N NCl + H — — OH N N— — OH + Cl + H 2O
(pH 9-10)
27. (i) Cationic Detergents : Cationic detergents are quarternary ammonium salts of amines with
acetates, chlorides or bromides as anions. Cationic part possess a long hydrocarbon chain and a
positive charge on nitrogen atom. Hence, these are called cationic detergents. Cetyltrimethylammonium
bromide is a popular cationic detergent and is used in hair conditioners.
+
é CH3 ù
ê ½ ú
ê ú
êCH3 (CH2 ) 15 ¾ N ¾ CH3 ú Br -
ê ½ ú
êë CH3 úû
Cetyltrimethyl ammonium bromide
Cationic detergents have germicidal properties and are expensive, therefore, these are of
limited use.
(ii) Food Preservatives: These are the chemical substances which are added to the food materials
to prevent their spoilage due to microbial growth and to retain their nutritive value for long
periods.
Preservatives prevent the rancidity of food and inhibit growth or kill the microganisms.
Examination Papers | 57
The most-common preservations used are, sugar table salt, sodium benzoate, Sodium
metabisulphite sorbic acid and propanoic acid.
(iii) Analgesics: Drugs which reduce or abolish pain without causing impairment of consciousness,
mental confusion, incoordination or paralysis or some other disturbances of nervous system.
These are classified as follow.
(a) Non-narcotic (non-addictive) analgesics: Aspirin, paracetamol etc.
(b) Narcotic drugs: These are known to be habit forming, e.g., morphine, Codeine, Heroin
etc.
28. (a) Molar Conductivity (Lm): It may be
defined as the conductance of a solution
containing 1 mole of electrolyte such that 400
the entire solution is placed is between two CH3COOH
Lm / (S cm mol )
–1
electrodes one centimeter apart.
2
Lm = k × v
or 200
k ´ 1000
Lm = KCl
M
Molar conductivity increases with decrease
in concentration or increase in dilution as
0 0.2 0.4
number of ions as well as mobility of ions 1/2 l/2
c / (mol / L)
increased with dilution.
For strong electrolytes the number of ions do not increase appreciably on dilution and only
mobility of ions increases due to decrease in inter-ionic attractions. Therefore L m increases a
little as shown in graph by a straight line.
For weak electrolyte the number of ions as well as mobility of ions increases on dilution as
shown by curve in the figure.
(b) At anode: Cu( s) ¾¾® Cu 2 + ( aq) + 2 e
0 × 0591 [Cu 2 + ]
Here E cell = E ocell - log
n [Ag + ] 2
Here E ocell = 0. 46 V, n = 2
E cell = 0.312 V
OR
1 æl ö
(a) k = ´ç ÷
R èAø
Where k = Conductivity
l
= Cell Constant
A
R = Resistance
k ´ 1000
Lm =
M
Where L m = Molar conductivity
k = Conductivity
M = Molarity of Solution
(b) At anode: Al( s) ¾¾®Al 3 + ( aq) + 3e ] ´ 2
0.0591 [Al 3 + ] 2
E cell = E ocell - log
n [ Ni 2 + ] 3
Here n = 6, [Al3+] = 0.001M = 1× 10–3M, [Ni2+] = 0.5M
E ocell = E o -Eo = - 0.25V - (-1.66V )
Ni 2 + / Ni Al 3+ / Al
E ocell = 1.41V
2
E ocell = 1.41 -
0.0591
log
10 -3 ( ) = 1.41 -
0.0591
log
10 -6
6 (0.5) 3 6 0.125
0.0591 0.0591
= 1.41 -
6
(
log 10 –6 ´ 8 =1.41 – ) 6
(
log10 –6 + log 2 3 )
0.0591 0.0591
= 1.41 - log (– 6 log 10 + 3 log2) = 1.41 – (– 6 + 3 ´ 0.3010 )
6 6
0.0591 0.3012
= 1.41 - ( -5.097) = 1.41 +
6 6
= 1.41 + 0.0502 = 1.4602V
E cell = 1.46 V
Examination Papers | 59
Fe 2 + ¾¾® Fe 3 + + e ] ´ 6
H2 S ¾¾® S + 2H+ + 2e - ] ´ 3
30. (a) (i) Cannizzaro reaction: Aldehyde which do not have an a - hydrogen atom, undergo
disproportionation reaction on treatment with concentrated alkali, In this reaction, one
molecule of aldehyde is reduced to alcohol while other is oxidised to carboxylic acid salt.
O
||
Conc.KOH
2H — C— H ¾ ¾¾¾¾® CH3 — OH + HCOOK +
Formaldehyde Methyl alcohol Potassiumformate
(ii) Clemmensen reduction: The carbonyl group of aldehyde and ketones is reduced to CH2
group on treatment with zinc amalgam and concentrated hydrochloric acid.
—O Zn/conc. HCl
C— + 4[H] CH2 + H2O
Aldehyde or Hydrocarbon
ketone
(b)
Element Percentage Atomic mass No. of moles Simplest molar
ratio
C 69.77 12 69 × 77 5 × 81
= 5 × 81 =5
12 1 ×16
H 11.63 1 11 × 63 11 × 63
= 11 × 63 = 10
1 1 ×16
O (100 – 81.4) = 18.60 16 18 × 60 1 ×16
= 1 ×16 =1
16 1 ×16
O
||
CH3 — C— CH2 — CH2 — CH3
Pentan -2-one
O
||
K 2 Cr2 O7
CH3 — C— CH2 — CH2 — CH3 ¾ ¾¾¾ ¾® CH3 — COOH + CH3 — CH2 — COOH
Pentan - 2 - one H 2 SO4 Ethanoic acid Propanoic acid
OR
–+
CH2—CH3 COOK COOH
+
KMnO4 – KOH H3 O
(a) (i)
D
O Benzoic acid
–
–
CH3 HC – OO —
– C — CH3
— C — CH
CHO
3
–
–
CrO3 O H3 O
+
(ii) O D
–
–
CH3 – C –
O Benzylidene Benzaldehyde
CH3 – C – diacetate
–
–
O
OR
CH3 CH(OCrOHCl2)2 CHO
CS2 +
H3 O
+ CrO2Cl2
–
–
C — Cl CHO
H2
(b) (i) Pd – BaSO4
+ HCl
–
–
O
— C — CH3
–
–
anhyd. AlCl3
(ii) + CH3 — C — Cl
Acetyl chloride
Benzene Acetophenone
O
O
–
–
–
–
C
— C — Cl
+ anhyd. AlCl3 + HCl
(iii)
l Disinfectants are chemical substances which kill micro-organisms or stop their growth but are
harmful to human tissues.
l Disinfectants are applied to inanimate objects such as floor, drainage system, instrument, etc.
l Chlorine in the concentration of 0.2 to 0.4 ppm in aqueous solution and SO2 in very low
concentration are disinfectants.
28. (a) (i) MnO-4 + 8H+ + 5e - ¾ ¾¾® Mn 2 + + 4H2 O
Fe 2 + ¾ ¾¾® Fe 3 + + e - ] ´ 5
2I - ¾ ¾¾® I 2 + 2e - ] ´ 3
H2 S ¾ ¾¾® S + 2H+ + 2e - ] ´ 3
0.0591 [Al 3 + ] 2
E cell = E ocell - log
n [ Ni 2 + ] 3
Here n = 6, [Al3+] = 0.001M = 1× 10–3M, [Ni2+] = 0.5M
E ocell = E o Ni 2 + / Ni -Eo Al
3+
/ Al = - 0.25V - (-1.66V )
E ocell = 1.41V
2
E ocell = 1.41 -
0.0591
log
10 -3 ( ) = 1.41 -
0.0591
log
10 -6
6 (0.5) 3 6 0.125
0.0591 0.0591
= 1.41 -
6
(
log 10 –6 ´ 8 =1.41 –
6
)log10 –6 + log 2 3 ( )
0.0591 0.0591
= 1.41 - log (– 6 log 10 + 3 log2) = 1.41 – (– 6 + 3 ´ 0.3010 )
6 6
0.0591 0.3012
= 1.41 - ( -5.097) = 1.41 +
6 6
= 1.41 + 0.0502 = 1.4602V
E cell = 1.46 V
OR
1 æl ö
(a) k= ´ç ÷
R èAø
Where k = Conductivity
l
= Cell Constant
A
R = Resistance
k ´ 1000
Lm =
M
Where L m = Molar conductivity
k = Conductivity
M = Molarity of Solution
(b) Fe( s) + Cd ( aq) l
2+
Fe 2 + ( aq) + Cd( s)
E ° cell
log k c = n
0.059
Here, n = 2
Examination Papers | 65
i = 2.42
24.
S. Complex Central Configuration Hybridisation Geometry Number of Magnetic
No. metal ion of metal ion of metal ion of the unpaired behaviour
complex electrons
27. (i) Antacids: Chemical substances which removes the excess acid in the stomach & raise the pH
to appropriate level, e.g., sodium hydrogen carbonate, a mixture of aluminium and magnesium
hydroxide, ranitidine, etc.
(ii) Non-ionic Detergents: Non-ionic detergents do not contain any ion in their constitution. One
such detergent is formed when stearic acid reacts with polyethylene glycol.
(iii) Antiseptics: These are the chemical substances which prevent the growth of micro-organisms
and may even kill them but are not harmful to living tissues. Antiseptics are applied to living
tissues such as wounds, cuts, ulcers. Dettol, soframicine are antiseptics.
66 | Xam idea Chemistry–XII
0.0591 [Al 3 + ] 2
E cell = E ocell - log
n [ Ni 2 + ] 3
Here n = 6, [Al3+] = 0.001M = 1× 10–3M, [Ni2+] = 0.5M
E ocell = E o Ni 2 + / Ni -Eo Al
3+
/ Al = - 0.25V - (-1.66V )
E ocell = 1.41V
2
E ocell = 1.41 -
0.0591
log
10 -3 ( ) = 1.41 -
0.0591
log
10 -6
6 (0.5) 3 6 0.125
0.0591 0.0591
= 1.41 -
6
(
log 10 –6 ´ 8 =1.41 –
6
)
log10 –6 + log 2 3 ( )
0.0591 0.0591
= 1.41 - log (– 6 log 10 + 3 log2) = 1.41 – (– 6 + 3 ´ 0.3010 )
6 6
0.0591 0.3012
= 1.41 - ( -5.097) = 1.41 +
6 6
= 1.41 + 0.0502 = 1.4602V
E cell = 1.46 V
CBSE EXAMINATION PAPERS
ALL INDIA–2009
Time allowed : 3 hours] [Maximum marks : 70
General Instructions:
(i) All questions are compulsory.
(ii) Question nos. 1 to 8 are very short answer questions and carry 1 mark each.
(iii) Question nos. 9 to 18 are short answer questions and carry 2 marks each.
(iv) Question nos. 19 to 27 are also short answer questions and carry 3 marks each.
(v) Question nos. 28 to 30 are long answer questions and carry 5 marks each.
(vi) Use log tables if necessary, use of calculators is not allowed.
11. Describe the underlying principle of each of the following metal refining methods: 2
(i) Electrolytic refining of metals
(ii) Vapour phase refining of metals.
12. Complete the following chemical reaction equations: 2
(i) XeF2 + H2O ¾
¾®
(ii) PH3 + HgCl2 ¾
¾®
13. Complete the following chemical reaction equations: 2
(i) MnO -4 (aq) + C2O 2- +
4 (aq) + H (aq) ¾
¾®
Cl
(ii) or Cl
(b) 100 mg of a protein is dissolved in enough water to make 100 mL of a solution. If this solution
has an osmotic pressure 13.3 mm Hg at 25° C, what is the molar mass of protein?
(R = 0.0821 L atm mol–1 K–1 and 760 mm Hg = 1 atm.)
OR
What is meant by:
(i) Colligative properties
(ii) Molality of a solution.
(b) What concentration of nitrogen should be present in a glass of water at room temperature?
Assume a temperature of 25° C, total pressure of 1 atmosphere and mole fraction of nitrogen in
air of 0.78. [KH for nitrogen = 8.42 × 10–7 M/mm Hg] 5
29. (a) Draw the structures of the following:
(i) H2S2O8
(ii) HClO4
(b) How would you account for the following:
(i) NH3 is a stronger base than PH3.
(ii) Sulphur has a greater tendency for catenation than oxygen.
(iii) F2 is a stronger oxidising agent than Cl2. 5
OR
(a) Draw the structures of the following:
(i) H2S2O7
(ii) HClO3
(b) Give an explanation for each of the following observations:
(i) In the structure of HNO3, the N – O bond
(121 pm) is shorter than the N – OH bond (140 pm)
(ii) All the P – Cl bonds in PCl5 are not equivalent.
(iii) ICI is more reactive than I2.
30. (a) Write chemical equations to illustrate the following name bearing reactions:
(i) Cannizzaro’s reaction
(ii) Hell-Volhard-Zelinsky reaction
(b) Give chemical tests to distinguish between the following pairs of compounds: 5
(i) Propanal and Propanone
(ii) Acetophenone and Benzophenone
(iii) Phenol and Benzoic acid
Examination Papers | 73
OR
(a) How will you bring about the following conversions:
(i) Ethanol to 3-hydroxybutanal
(ii) Benzaldehyde to Benzophenone.
(b) An organic compound A has the molecular formula C8H16O2. It gets hydrolysed with dilute
sulphuric acid and gives a carboxylic acid B and an alcohol C. Oxidation of C with chromic
acid also produced B. C on dehydration reaction gives but-1-ene. Write equations for the
reactions involved.
(ii) [NiCl 4 ] 2-
(iii) [CoFe 6 ] 3-
[At. Nos,: Ni = 28; Co = 27]
27. What are the following substances? Give one example of each of them. 3
(i) Cationic detergents
(ii) Enzymes
(iii) Sweetening agents
30. (a) Draw the structures of the following:
(i) XeF4
(ii) H2S2O7
(b) Explain the following observations:
(i) Phosphorus has a greater tendency for catenation than nitrogen.
(ii) The negative value of electron gain enthalpy is less for fluorine than that for chlorine.
(iii) Hydrogen fluoride has a much higher boiling point than hydrogen chloride. 5
OR
(a) Draw the structures of the following:
(i) PCl5(s)
(ii) SO2-
3
SOLUTIONS
CBSE (All India) SET–I
1. Metallic substances conduct electricity through electrons while ionic substances conduct electricity in
molten state or in solution through ions.
2. The process of settling of colloidal particles is called coagulation.
3. It is a thermal process of extracting a metal from its ore.
4. This is due to polymeric structure of red phosphorus or angular strain in P4 molecule of white
phosphorus where the angle is only 60°.
5. H2C = CH – CH – CH2 – CH2 – CH3 Hex-l-en-3-ol.
|
OH
O
||
6. 1-Phenyl pentan-1-one CH3—CH2—CH2—CH2—C—
At anode: Sn 2 + ¾
¾® Sn 4 + ( aq) + 2e - ] ´ 5 E° = + 0.15 V
Eo = -E o = -0.15 V
Sn 4 + /Sn 2 + Sn 2 + /Sn 4 +
= 1.51 – (– 0.15)
E oCell = 1 . 66V
As E ocell is +ve therefore the reaction will take place in forward direction, i.e., favours the formation of
products.
Examination Papers | 77
10. (i) Elementary step: Each step of a complex reaction is called an elementary step.
(ii) Rate of reaction: It is the change in the concentration of any of the reactants or products per
unit time.
11. (i) Electrolytic refining: In this method, the impure metal is made to act as anode. A strip of
same metal in pure form is used as cathode. They are put in a suitable electrolytic bath
containing soluble salt of same metal. When electric current is passed, the metal from the
anode goes into solution as ions due to oxidation while pure metal gets deposited at the
cathode due to reduction of metal ions. The less electropositive impurities settle down below
the anode as anode mud.
¾® M n + + ne -
At anode: M ¾
At cathode: M n + + ne - ¾
¾® M
(ii) Vapour phase refining of metals: In this method, crude metal is freed from impurities by first
converting it into volatile compound and collected elsewhere. It is then decomposed to give
pure metal. For example refining of nickel by Mond process.
330 - 350K
Ni + 4CO ¾ ¾ ¾ ¾
¾® Ni(CO) 4
impure Tetracarbonyl nickel (volatile)
450 - 470K
Ni(CO) 4 ¾ ¾ ¾ ¾
¾® Ni + 4CO
Pure
C 2 O24 - ¾® 2CO2 + 2e - ] ´ 5
¾
Fe 2 + ¾® Fe 3 + + e - ] ´ 6
¾
Cr2 O72 - + 6Fe 2 + + 14H+ ¾
¾® 2Cr 3 + + 6Fe 3 + + 7H2 O
14. (i) Cl 3° halide reacts faster than 2° halide because of the greater stability of tertiary carbocation.
tert-Butyl
chloride
Cl
(ii) 2° halide reacts faster than 1° halide because of the greater stability of
sec-Hexyl chloride secondary carbocation than primary.
CH3 CH3
15. (i) I
+ HI
I–lodo–1–methyl cyclohexane
78 | Xam idea Chemistry–XII
16. The four bases present in DNA are adenine (A), guanine (G), cytosine(C) and thymine (T).
Thymine(T) is not present in RNA.
17.
Fat soluble vitamins Sources Deficiency diseases
Vitamin A Fish liver oil, carrots, milk Xerophthalmia, Night blindness.
Vitamin D Exposure to sunlight, fish and egg. Rickets and osteomalacia.
Vitamin E Vegetable oils like wheat germ oil, Sterility and muscular atrophy
sunflower oil, etc.
Vitamin K Green leafy vegetables Haemorrhages and increased blood
clotting time.
18.
Thermoplastics Thermosetting plastics
(i) These polymer are linear or slightly branched (i) These polymers are cross linked or heavily
chain molecules branched molecules
(ii) Soften on heating and harden on cooling and (ii) On heating undergo extensive cross linking in
can be remoulded. moulds and become infusible.
(iii) Some common examples are polyethene, (iii) Some common examples are bakelite,
PVC, polystyrene, etc. urea-formaldehyde resins, terylene, etc.
n = 2, [ Ag + ] = ?
Given, E cell = 4.22 V [Cu 2+ ] = 0.1 M
Eo = 0.80 V Eo = 0.34 V
Ag + /Ag Cu 2 + /Cu
0.0591 [Cu 2 + ]
E cell = E ocell - log
n [Ag + ]
0 . 0591 0 .1
0.422 = 0.46 – log
2 [Ag + ] 2
10 -1
0.422 – 0.46 = – 0.0295 log
[ Ag + ] 2
10 -1
– 0.038 = – 0.0295 log
[ Ag + ] 2
0.038
= log10 -1 - log[ Ag + ] 2
0.0295
1.2881 = – log 10 – 2 log [Ag+]
1.2881 = – 1 – 2 log [Ag+]
2 log [Ag +] = 2.2881
log [Ag +] = – 1.144
[Ag+] = Antilog 2.856
[Ag+] = 7.178 × 10–2 M
80 | Xam idea Chemistry–XII
22. (i) The positively charged colloidal particles of Fe(OH)3 get coagulated by the negatively charged
ions provided by electrolyte.
(ii) The path of light becomes visible due to scattering of light by colloidal particles (Tyndall
effect).
(iii) Electrophoresis takes place in which colloidal particles move towards the oppositely charged
electrode where they lose their charge and get coagulated.
23. (i) Crystal field spliting: When the ligands approach the central metal ion, the electrons in the
d-orbitals of central metal ion will be repelled by the lone pairs of the ligands. Because of these
interactions the degeneracy of d orbitals of the metal ion is lost and these split into two sets of
orbitals having different energies. This is known as crystal field splitting, e.g., for d4,
configuration is t32g e1g in the presence of weak field ligand.
(ii) Linkage isomerism: The isomers which have same molecular formula but differ in the linkage
of ligand atom to the central metal atom are called linkage isomers, e.g.,
[Co(NH3 ) 5 NO2 ]Cl 2 and [Co(NH3)5ONO]Cl2
Pentaamminenitrito–N–Cobalt (III) chloride, pentaamminenitrito–O–Cobalt(III) chloride
(iii) Ambidentate ligand: A ligand which can bind to the central metal atom through any of the
two donor atoms present in it is called ambidentate ligand, e.g., NO2 can bind to metal either
O
through nitrogen, i.e., as nitrito-N ( N ) or through oxygen atom, i.e., as nitrito –O
O
(¬ O—N=O)
OR
Complex/Ion Central Configu- Hybri- Geometry Number Magnetic
metal ration of disation of of the of behaviour
ion/atom metal ion metal ion complex unpaired
involved electrons
[Co(NH3)6]3+ Co3+ d64s0 d2sp3 octahedral 0 Diamagnetic
3+ 3+ 3 0
[Cr(NH3)6] Cr 3d 4s d2sp3 octahedral 3 Paramagnetic
3 2 3
[Ni(CO)4] Ni 3d 4s sp Tetrahedral 0 Diamagnetic
24. (i) Ethanol undergoes intermolecular hydrogen bonding due to the presence of a hydrogen
attached to oxygen atom. As a result, ethanol exist as associated molecules and hence it has
higher boiling point than methoxy ethane which does not form hydrogen bonds.
(ii) Phenol is stronger acid than ethanol because the phenoxide ion left after the release of proton is
stabilized by resonance but ethoxide ion is not. Moreover, ethoxide ion is destabilised by +I
effect of ethyl group.
(iii) Due to –I effect or –R effect of –NO2 group, the resulting phenolate ion is more stable than
phenoxide ion. Therefore o- and p--nitrophenols are more acidic than phenol.
25. (i) The catalytic activity of transition metals is attributed to the following reasons:
(a) Because of their variable oxidation states transition metals form unstable intermediate
compounds and provide a new path with lower activation energy for the reaction.
Examination Papers | 81
(b) In some cases, the transition metal provides a suitable large surface area with free
vacancies on which reactants are adsorbed.
(ii) This due to filling of 4f orbitals which have poor shielding effect or due to lanthanoid contraction.
(iii) This is due to comparable energies of 5f, 6d and 7s orbital in actinoids.
O
||
26. (i) R — C— NH2 ¾LiAlH ¾¾ ¾4
® R — CH2 — NH2
H2O 1°amine
+ –
N2Cl
Benzene Benzene
diazonium chloride
NH2 NH2
Br Br
+ 3Br2(aq) + 3HBr
Aniline
Br
2, 4, 6 – Tribromo aniline
27. (i) Non-ionic detergents: These are the esters of high molecular mass alcohols with fatty acids.
These are named so because they do not contain any ion in their constitution, e.g.,
polyethylene glycol stearate.
(ii) Food preservatives: These are the substances which prevent spoilage of food due to microbial
growth, e.g., sodium benzoate, potassium metabisulphite, salts of sorbic acid and propanoic
acid, etc.
(iii) Disinfectants: These are the chemical substances which kill micro-organisms or stop their
growth but are harmful to human tissues, e.g., phenol (1%), chlorine in concentration of 0.2 to
0.4 pm in aqueous solution, SO2, etc.
28. (a) (i) Mole fraction: It may be defined as the ratio of number of moles of one component to the total
number of moles of all the components present in the solution.
(ii) Van’t Hoff factor (i): It may be defined as the ratio of normal molar mass to the observed
molar mass, i.e., Van’t Hoff factor
Normal molar mass
i=
Observed molar mass
OR
Observed colligative property
i=
Calculated colligative property
WB ´ R ´ T
(b) p =
M B ´V
82 | Xam idea Chemistry–XII
WB ´ R ´ T
MB=
p´ V
Here
WB = 100 mg = 100 × 10–3 g
R = 0.0821 L atm K–1 mol–1
T = 25°C = (25 + 273) K = 298K
V = 100 mL = 10 × 10–3 L
13.3
p = 13.3 mm Hg = atm
760
100 ´ 10 -3 g ´ 0.0821 L atm K -1 mol -1 ´ 298K
MB =
13.3
atm ´ 100 ´ 10 -3 L
760
100 ´ 10 -3 ´ 0.0821 ´ 298 ´ 760 g mol -1 18594 g mol -1
MB = =
13.3 ´ 10 ´ 10 -3 133
M B = 1398.286 g mol–1
OR
(i) Colligative properties: Those properties which depend on the number of solute particles
irrespective of their nature relative to the total number of particles present in the solution are
called colligative properties of solutions.
(ii) Molality (m): It is the number of moles of the solute per kilogram of the solvent and is
expressed as
Moles of solute
Molality =
Mass of solvent in kg
(b) PN 2 = 0.78 atm = 0.78 × 760 mm Hg
= 592.8 mm Hg
KH = 8.42 × 10–7 M/mmHg
X N2 = ?
X N 2 = KH × PN 2
= 8.42 × 10–7 M/mmHg × 592.8 mmHg = 4991.376 × 10–7
X N 2 = 4.99 × 10 -4
X N2 X N2
X N2 = =
X N2 + X H2O X H2O
1000
X N2 = X H2O ´ X N2 = ´ 4.99 ´ 10 -4 = 0.0277
18
X N 2 = 2.77 × 10–2 = 2.77 × 10–2M
Examination Papers | 83
O O
29. (a) ( i) S S
O O
O OH O
HO
Peroxodisulphuric acid
(H2S2O8)
H
O
(ii) Cl
O
O
O
Perchloric acid
(HClO4)
(b) (i) This is because the lone pair of electrons on N atom in NH3 is directed and not delocalised as it
in PH3 due to larger size of P.
(ii) This is because S-S single bond is stronger O—O single bond.
(iii) Due to small size of fluorine atom there are strong interelectric repulsions in the relatively
small size 2p orbitals of fluorine and thus, the incoming electron does not experience much
attraction.
OR
H
O O O
(a) ( i) S S (ii) Cl
O
O O O
OH HO O
(i) Due to resonance, N—O bond length is the average of single and double bond whereas
N—OH bond is purely single bond.
(ii) PCl5 has trigonal bipyramidal structure in which the three equatorial P—Cl bonds are
equivalent, while the two axial bonds are longer than equational bonds. This is due to the
fact that axial bond pairs suffer more repulsion as compared to equatorial bond pairs.
(iii) This is because I—Cl bond has lower bond dissociation enthalpy than Cl—Cl bond.
84 | Xam idea Chemistry–XII
3C 6 H5 COOH + FeCl 3 ¾
¾® (C 6 H5 — COO) 3 Fe + 3HCl
Ferric benzoate
(Buff coloured ppt)
OR
OH
|
(i) CH3 — CH2 — OH ¾PCC dil NaOH
¾
¾® CH3 — CHO ¾ ¾ ¾¾® CH3 — CH— CH2 — CHO
Ethanal Ethanol 2 - Hydroxy butanal
Examination Papers | 85
(ii) O OMgBr O
C—H H—C—CH3 CH—CH3
Aceto phenon
(b) A = Butyl butanoate B = Butanoic acid
C = Butanol D = But–1–ene
Reactions involved:
O
||
H 2 SO4
CH3 — CH2 — CH2 — C— O — CH2 — CH2 — CH2 — CH3 + H2 O ¾ ¾ ¾
¾®
Butylbutanoate(A)
O
||
CH3 — CH2 — CH2 — C— OH + CH3 — CH2 — CH2 — CH2 — OH
Butanoic acid(B) Butanol(C)
(O) (O)
CH3 — CH2 — CH2 — CH2 — OH ¾ ¾® CH3 — CH2 — CH2 — CHO ¾ ¾®
Butanol(C) H 2 CrO4
CH3 — CH2 — CH2 — COOH
Butanolic acid (B)
conc.H SO
CH3 — CH2 — CH2 — CH2 — OH ¾ ¾ ¾2¾¾
4
® CH3 — CH2 — CH = CH2 + H2 O
Butan –1– ol Heat But–1– ene.
z´ M
NA = , we get
a3 ´ d
2 ´ 56 g mol –1
NA =
( 286.65 ´ 10 -10 cm) 3 ´ 7.87 g cm –3
= 6.042 × 1023 mol–1
k2 E a æ T2 - T1 ö
20. log = ç ÷
k1 2.303R çè T1 T2 ÷ø
2.303 ´ R ´ T1 ´ T2 k
Ea = log 2
T2 – T1 k1
(ii) Benzoic acid being an acid, decomposes NaHCO3 to produce brisk effervescence due to
evolution of CO2 while ethyl benzoate does not.
– +
C 6 H5 — COOH+ NaHCO3 ¾
¾® C 6 H5 — CO O N a + CO2 + H2 O
Benzoic acid Sodium benzoate
(b)
Element Percentage Atomic mass No. of moles Simplest
molar ratio
C 69.77 12 69 × 77 5 × 81
= 5 × 81 =5
12 1×16
H 11.63 1 11× 63 11× 63
= 11× 63 = 10
1 1×16
O (100 – 81.4) = 18.60 16 18 × 60 1×16
= 1×16 =1
16 1×16
Empirical formula of the compound A = C5 H10 O
Molecular formula of the compound A = n (Empirical formula)
Molecular mass of compound A
n=
Empirical formula mass of compound A
Molecular mass of compound A = 86
Empirical formula mass of compound A = 5 ´ 12 + 1´ 10 + 1´ 16
= 60 + 10 + 16
= 86
86
n= =1
86
Molecular formula of the compound A = 1(C5 H10 O)
= C5 H10 O
As the compound A forms addition compound with NaHSO3 therefore it must be either an
aldehyde or ketone.
As it does not reduce Tollens reagent and give positive Iodoform test therefore it must be a
methyl ketone.
As on oxidation the compound A gives a mixture of ethanoic acid and propanoic acid,
therefore compound A is
O
||
CH3 — C— CH2 — CH2 — CH3
Pentan -2-one
The chemical reactions are:
O OH
|| |
CH3 — C— CH2 — CH2 — CH3 + NaHSO3 ¾ ¾® CH3 — C — CH2 — CH2 — CH3
Pentan -2-one |
+
SO-3 N a
Sodium hydrogen sulphite addition product
88 | Xam idea Chemistry–XII
O
||
CH3 — C— CH2 — CH2 — CH3 + 3I 2 + 4NaOH
Pentan - 2 - one
- +
Iodoform
¾ ¾ ¾¾® CHI 3 ¯ + CH3 — CH2 — CH2 — CO O Na + 3NaI + 3H2 O
reaction (Iodoform yellow ppt)
O
||
K 2 Cr2 O7
CH3 — C— CH2 — CH2 — CH3 ¾ ¾ ¾¾® CH3 — COOH + CH3 — CH2 — COOH
Pentan - 2 - one H 2 SO4 Ethanoic acid Propanoic acid
OR
(a) (i) Acid strength: 4-Methoxy benzoic acid <Benzoic acid < 4-Nitrobenzoic acid
< 3, 4-Dinitrobenzoic acid.
(ii) Acid strength: (CH3)2CHCOOH < CH3CH2CH2COOH < CH3CH(Br)CH2COOH
< CH3CH2CH(Br)COOH
O OH
|| |
LiAlH 4 Conc.H SO4
(b) (i) CH3 — C— CH3 ¾ ¾ ¾¾® CH3 — CH — CH3 ¾ ¾ ¾ 2¾¾ ® CH3 — CH = CH2
Propanone Propan - 2 - ol Heat Propene
COOH COCl CHO
PCl5 H2
(ii) Pd/BaSO4,S
OH
Br MgBr CH—CH3
O
Mg (i) CH3—C—H
(iii) dry ether (ii) H2O
OR
O
O O O O O O F F
(a) (i) N N N N (ii) XeOF4:
O O O O
Xe
(N2O5)
F F
Square pyramidal
(b) (i) Due to small size of oxygen atom there will be greater interelectronic repulsions in oxygen.
(ii) Due to non-availability of d orbitals in valence shell nitrogen does not form pentahalide.
(iii) Due to low bond dissociation enthalpy of H-I as compared to H—Cl.
At cathode: Ni 2 + ( aq) + 2e ¾
¾® Ni ( s)] ´ 3
0.0591 [ Al 3 + ] 2
E cell = E ocell - log
n [ Ni 2 + ] 3
Here n = 6, [Al3+] = 0.001M = 1× 10–3M, [Ni2+] = 0.5M
E ocell = E o Ni 2 + / Ni -Eo Al
3+
/ Al = - 0.25V - (-1.66V )
E ocell = 1.41V
2
E ocell = 1.41 -
0.0591
log
10 -3 ( ) = 1.41 -
0.0591
log
10 -6
6 (0.5) 3 6 0.125
0.0591 0.0591
= 1.41 -
6
(
log 10 –6 ´ 8 =1.41 –
6
)
log10 –6 + log 2 3 ( )
0.0591 0.0591
= 1.41 - log (– 6 log 10 + 3 log2) = 1.41 – (– 6 + 3 ´ 0.3010 )
6 6
0.0591 0.3012
= 1.41 - ( -5.097) = 1.41 +
6 6
= 1.41 + 0.0502 = 1.4602V
E cell = 1.46 V
23. (i) Ni in its atomic ionic state can not afford two vacant 3d orbitals hence d 2 sp 3 hybridisation is
not possible.
(ii) Transition metals have vacant d orbitals in their atoms or ions into which the electron pairs can
be donated by ligands containing p electrons, e.g., C6H6, CH2 = CH2, etc. Thus dp - Pp
bonding is possible.
(iii) Because in case of CO back bonding takes place in which the central metal uses its filled d
orbital with empty anti bonding p* molecular orbital of CO.
OR
27. (i) Cationic detergents: These are quarternary ammonium salts of amines with acetates,
chlorides or bromides as anions, e.g., cetyltrimethylammonium bromide.
(ii) Enzymes: Enzymes are globular proteins with high molecular mass ranging from 15,000 to
1,000,000 g mol–1, and form colloidal solution in water. A number of reactions that occur in
the body of animals and plants to maintain the life process are catalysed by enzymes therefore
enzymes are termed as biochemical catalysts.
(b) Sweetening agents: These are non-nutritive substances which are used as substitute of sugar
in food and beverages, e.g., ortho-sulphobenzimide (saccharin), sucrolose, aspartame, etc.
F F O O
30. (a) (i) Xe (ii) S S
O O
O OH
F F OH
Pyrosulphuric acid
Square planar
(XeF4) (H2S2O7)
(b) (i) This is because P–P single bond is stronger than the N–N single bond.
(ii) Due to extremely small size of F atom, interelectronic repulsions are more in fluorine.
(iii) There is H-bonding in HF molecules due to high electronegativity and small size of
fluorine atom but there is no H-bonding in HCl.
OR
Cl + Cl –
Cl Cl
P
(a) (i) Cl Cl P (ii) S –
O
O –
Cl Cl
O
Cl Cl (SO32– )
PCl5(s)
(b) (i) Due to small size and high electronegativity of nitrogen, molecules of ammonia are
highly associated through hydrogen bonding.
(ii) This is due to small size and high ionization enthalpy of helium.
(iii) As Bi(V) is more stable than Sb(V) due to inert pair effect.
CBSE EXAMINATION PAPERS
FOREIGN–2009
Time allowed : 3 hours] [Maximum marks : 70
General Instructions:
(i) All questions are compulsory.
(ii) Question nos. 1 to 8 are very short answer questions and carry 1 mark each.
(iii) Question nos. 9 to 18 are short answer questions and carry 2 marks each.
(iv) Question nos. 19 to 27 are also short answer questions and carry 3 marks each.
(v) Question nos. 28 to 30 are long answer questions and carry 5 marks each.
(vi) Use log tables if necessary, use of calculators is not allowed.
21. Calculate the freezing point depression for 0.0711 m aqueous solution of sodium sulphate, if it is
completely ionised in solution. If this solution actually freezes at – 0.320 °C, what is the value of Van’t
Hoff factor for it at the freezing point? (Kf for water is 1.86°C mol–1) 3
22. Describe what is observed when 3
(i) an electric current is passed through a colloidal solution.
(ii) a beam of light is passed through a colloidal solution.
(iii) an electrolyte such as NaCl, is added to hydrated ferric oxide sol.
94 | Xam idea Chemistry–XII
H
(i)
+ HBr
H H
CH3
(ii) + HI
O
C
Anhydrous AlCl3 Ar/R
+ ........
(ii)
O
C
.............
(iii) + ........ 5
OR
(a) How will you bring about the following conversions:
(i) Ethanol to 3-hydroxybutanal
(ii) Benzaldehyde to benzophenone
(b) An organic compound A contains 69.77% carbon, 11.63% hydrogen and the rest oxygen. The
molecular mass of the compound is 86. It does not react with Tollen’s reagent but forms an
addition compound with sodium hydrogen sulphite and gives a positive iodoform test. On
vigorous oxidation it gives a mixture of ethanoic and propanoic acids. Derive the structure of
compound A.
29. (a) Complete the following reaction equations:
(i) XeF2 + PF5 ¾
¾®
30. (a) A reaction is of second order with respect to a reactant. How is the rate of reaction affected if
the concentration of this reactant is
(i) doubled, (ii) reduced to half?
(b) A first order reaction has a rate constant of 0.0051 min–1. If we begin with 0.10 M
concentration of the reactant, what will be the concentration of the reactant left after 3 hours? 5
OR
(a) Define the following:
(i) Rate of reaction. (ii) Elementary step in a reaction
(b) For a decomposition reaction, the values of rate constant k at two different temperature are
given below:
k1 = 2.15 × 10–8 L mol–1 s–1 at 650 K
k2 = 2.39 × 10–7 L mol–1 s–1 at 700 K
Calculate the value of activation energy (Ea) for this reaction. (R = 8.314 J K–1 mol–1)
Rate = k[PH3]
The half-life of PH3 is 37.9 s at 120°C.
(i) How much time will be required for 3/4 of PH3 to decompose?
(ii) What fraction of the original amount of PH3 will remain undecomposed after 1 minute? 5
OR
Hydrogen peroxide, H2O2 (aq) decomposes to H2O(l) and O2(g) in a reaction that is of first order in
H2O2 and has a rate constant, k = 1.06 × 10–3 min–1.
(i) How long will it take 15% of a sample of H2O2 to decompose?
(ii) How long will it take 85% of a sample of H2O2 to decompose?
(iii) The +5 oxidation state becomes less stable down the group in group 15 of the periodic
table. 5
OR
(a) Complete the following reaction equations:
(i) P4 + NaOH + H2O ¾
¾®
(ii) Cu + HNO3 (dilute) ¾
¾®
(b) Explain why
(i) H2O is a liquid while, inspite of a higher molecular mass, H2S is a gas.
(ii) iron dissolves in HCl to form FeCl2 and not FeCl3.
(iii) helium is used in diving equipment
Examination Papers | 99
SOLUTIONS
CBSE (Foreign) SET–I
1
1. 8 (Corner atoms) × + 1 (body centre atom) × 1 = 1 + 1 = 2
8
2. Emulsion is a colloidal solution in which both the dispersed phase and dispersion medium are liquids
e.g. milk, cod liver oil, etc.
3. Sulphur.
CH3Br
4. CH3—CH = C—CH—CH3 : 4–Bromo–3–methylpent–2–ene.
O O
|| ||
5. 3–oxopentanal: CH3 — CH2 — C— CH2 — C— H
6. Aluminium occurs as Al2O3.2H2O
Iron occurs as Fe2O3
7. NH3 < R–NH2 < R3N < R2NH
8. Ranitidine (zantac).
9. Molality is the number of moles of solute per thousand grams of solvent whereas molarity is the
number of moles of solute dissolved in one litre of solution.
Molality is independent of temperature whereas molarity changes with change in temperature as
volume changes with temperature.
10. (i) Dilute NaCN forms a soluble complex with Ag or Ag2S while the impurities remain unaffected
which are filtered off.
4Ag + 8NaCN + O2 + 2H2O ¾
¾® 4Na[Ag(CN2)] + 4NaOH
Or Ag2S + 4NaCN ¾
¾® 2Na[Ag(CN) 2 ] + Na 2 S
Sodium dicyanoargentate(I)
(Soluble complex)
(ii) Carbon monoxide forms a volatile complex, nickel tetracarbonyl with nickel which on
decomposition gives pure nickel.
330– 350K
Ni + 4CO ¾ ¾ ¾ ¾
¾® Ni(CO) 4
Impure Nickel tetracarbonyl
450 - 470K
Ni(CO) 4 ¾ ¾ ¾ ¾
¾® Ni + 4CO
Pure
At cathode : Reduction of oxygen in the presence of H+ ions. The H+ ions are produced by
either H2 O or H2 CO3 (formed by dissolution of CO2 in moisture)
2H+ ( aq) + 2e - ¾ ¾
¾® 2H
100 | Xam idea Chemistry–XII
1
2H + O ( g) ¾ ¾¾® H2 O
2 2
Net reaction at cathodic area
1
2H+ ( aq) + O2 + 2e - ¾¾® H2 O E° H + /O /H O = 1.23V
2 2 2
(ii) S S O
O
O OH
OH
Pyrosulphuric acid
(H2S2O7)
Examination Papers | 101
13. (i) This is because, transition elements have strong metallic bonds due to presence of large
number of unpaired electrons.
(ii) This is because in transition elements incoming electron goes into d-orbitals of inner shell
whereas in main group elements, the incoming electron goes to outermost shell.
14. (i) Williamson’s Synthesis:
CH3 CH3
CH3—C—ONa+CH3—Br CH3—C—O—CH3+NaBr
CH3 CH3
Sodium tert-butoxide Methyl tert-butyl (ether)
H H H H H
+ Fast +
H— C — C — O — H + H H— C — C — O — H
H H H H
Ethyl alcohol Ethyl oxonium ion
15. H+
(i) CH3 — CH2 — OH ¾ ¾® CH2 CH2 + H2 O
D
Mechanism
Step I: Formation of carbocation: It is the slowest step and hence, the rate determining step.
H H H H H
+ Slow +
H— C — C — O — H H— C — C + H2O
H H H H
Ethyl oxonium ion Ethyl carbocation
Alkene H OH
Mechanism
Step I: Protonation of alkene to form carbocation by electrophilic attack of H3O+.
+
H2O + H H3O +
H H
+ +
—C
C— + H—O—H —C—C + H2O
l
+ +
—C—C + H2O —C—C—O—H
17. (i) Invert Sugar: Sucrose is dextrorotatory, on hydrolysis in the presence of HCl or enzyme
invertase, it produces a mixture of D–C(+)–glucose and D–(–)–fructose which is laevorotatory
called invert sugar.
(ii) Polypeptide: If more than ten a-amino acids are joined together by peptide bond (–CONH–)
the polyamide thus formed is called polypeptide.
18. (i) This is because the Ca2+ and Mg2+ ions present in hard water get precipitated as calcium and
magnesium soap which being insoluble stick to the clothes as gummy mass.
(ii) This is because detergents can be used in hard water as well as in acidic solutions, as sulphuric
acid and their calcium and magnesium salts are soluble in water but the fatty acids and their
calcium and magnesium salts are insoluble.
Examination Papers | 103
OR
O O
|| ||
n HO — C — CH2 — CH2 — C— OH + n H2 N — CH2 — CH2 — NH2
¯
éO O ù
ê| | || ú
—êC— CH2 — CH2 — C — HN — CH2 — CH2 — NHú— + 2nH2 O
ê ú
êë úû n
i = 2 × 42
104 | Xam idea Chemistry–XII
22. (i) Electrophoresis takes place in which colloidal particles move towards the oppositely charged
electrode where they lose their charge and get coagulated.
(ii) The path of light becomes visible due to scattering of light by colloidal particles (Tyndall
effect).
(iii) The positively charged colloidal particles of Fe(OH)3 get coagulated by the negatively charged
ions provided by electrolyte.
23. (i) Cr 2+ is reducing as its configuration changes from d 4 to d 3 , the latter having a half filled t2g
configuration. On the other hand, the change from Mn 3+ to Mn 2+ results in the half-filled d 5
configuration which has extra stability therefore Mn 3+ is oxidising.
(ii) Because the high hydration enthalpy of Cu 2+ easily compensates the second ionization
enthalpy of Cu.
(iii) This is because manganese has electronic configuration [Ar]3d54s2, with five unpaired
electrons in 3d orbitals.
24. NH3 3+ NH3 3+ 3+
H 2N H 3N en
H 2O
CO en CO en CO
H 2O H 2O H 3N OH2
H 2O NH3 OH2
Chiral Chiral Chiral
(i) (ii) (iii)
H +H—Br Br H
25. (i)
H H
H H H
1–Bromo–1–phenyl–ethane
CH3 CH3
I
(ii) + HI
1–Iodo–1–methyl cyclohexane
Chlorocylohexane
+ — + –
NH2 N2Cl N2BF4 NO2
Aniline Nitrobenzene
Examination Papers | 105
O O
|| ||
(ii) CH3 — CH2 — NH2 + CH3 — C— Cl ¾
¾® CH3 — C— NH — CH2 — CH3 + HCl
Ethanamine Ethanoyl chloride N – Ethyl ethanamine
OR
(i) Methylamine on treatment with alcoholic KOH and CHCl3 gives offensive smell of methyl
isocyanide but dimethyl amine does not.
CH3 — NH2 + CHCl 3 + 3KOH ¾
¾® CH3 — CH2 — NC + 3KCl + 3H2 O
Methyl amine (alc) Ethyl isocyanide
(1°amine) (Offensive smell)
CHCl /KOH
(CH3 ) 2 NH ¾ ¾ ¾3 ¾¾® No reaction.
Dimethyl amine D
(2 °amine)
(ii) Aniline on treatment with NaNO2/HCl (HNO2) at 0–5°C followed by treatment with an
alkaline solution of b -naphthol gives an orange coloured azodye while benzylamine does not
give this test.
OH
NaNO2/HCl + – b-Naphthol
NH2 N = NCl dil NaOH N = N—
0–5°C
Aniline
Orange dye
(iii) Add Br2(aq), aniline forms white ppt while ethyl amine does not form such ppt.
NH2 NH2
Br Br
+3Br2(aq) +3HBr
Aniline
Br
2, 4, 6–Tribromo aniline
(white ppt)
27.
Addition Polymerisation Condensation Polymerisation
(i) Monomers are unsaturated molecules (i) Monomers have di or polyfunctional groups.
(ii) Involves chain reaction (ii) Does not involve chain reaction.
(iii) Formed by adding monomers to a growing (iii) Monomers combine together with the loss of
chain without loss of any molecules. molecules like H2O, NH3, etc.
Examples: Polyethene, Polystyrene, Teflon Examples: Terylene, Bakelite, Nylon-66, etc.
etc.
106 | Xam idea Chemistry–XII
+
KMnO4 – KOH H3 O
D
Benzoic acid
O
(ii)
–
–
CH3 HC – OO —
– C — CH3
— C — CH
CHO
3
–
–
CrO3 O H3 O
+
O D
–
–
CH3 – C –
O Benzylideue Benzaldehyde
CH3 – C – diacetate
–
–
O
OR
CH3 CH(OCrOHCl2)2 CHO
CS2 +
H3 O
+ CrO2Cl2
C — Cl CHO
H2
(b) (i) Pd – BaSO4
+ HCl
O
–
–
O
— C — CH3
–
–
anhyd. AlCl3
(ii) + Ar/R — C — Cl
Acetyl chloride
Benzene Acetophenone
O
O
–
–
–
–
C
— C — Cl
+ anhyd. AlCl3 + HCl
(iii)
OR
OH
|
PCC dil NaOH
(a) (i) CH3 — CH2 — OH ¾ ¾
¾® CH3 — CHO ¾ ¾ ¾¾® CH3 — CH— CH2 — CH3
Ethanol Ethanol 2 - Hydroxy
butanol
(ii) O OMgBr OH
C—H H—C—C6H5 CH—C6H5
+ C6H5—MgBr H2O/H+
Benzaldehyde
(O) K2Cr2O7/H2SO4
O
C—C6H5
Benzophenone
(b)
Element Percentage Atomic mass No. of moles Simplest molar
ratio
C 69.77 12 69 × 77 5 × 81
= 5 × 81 =5
12 1 ×16
H 11.63 1 11 × 63 11 × 63
= 11 × 63 = 10
1 1 ×16
O (100 – 81.4) = 18.60 16 18 × 60 1 ×16
= 1 ×16 =1
16 1 ×16
86
n = =1
86
Molecular formula of the compound A = 1(C5 H10 O)
= C5 H10 O
As the compound A forms addition compound with NaHSO3 therefore it must be either an
aldehyde or ketone.
As it does not reduce Tollens reagent and give positive iodoform test therefore it must be a methyl
ketone.
As on oxidation the compound A gives a mixture of ethanoic acid and propanoic acid,
therefore compound A is
O
||
CH3 — C— CH2 — CH2 — CH3
Pentan -2-one
O
||
CH3 — C— CH2 — CH2 — CH3 + 3I 2 + 4NaOH
Pentan - 2 - one
- +
Iodoform
¾ ¾ ¾¾® CHI 3 ¯ + CH3 — CH2 — CH2 — CO O Na + 3NaI + 3H2 O
reaction (Iodoform yellow ppt)
O
||
K Cr2 O7
CH3 — C— CH2 — CH2 — CH3 ¾ ¾2 ¾¾ ® CH3 — COOH + CH3 — CH2 — COOH
Pentan - 2 - one H 2 SO4 Ethanoic acid Propanoic acid
OR
(a) (i) PCl5 + 4H2O (excess) ¾
¾® H3PO4 + 5HCl
¾® 4H+(aq) + 4F–(aq) + O2(g)
(ii) 2F2(g) + 2H2O(l) ¾
(b) (i) This is due to small size, high ionisation enthalpy and stable electronic configuration of
helium.
(ii) This is because P–P single bond is stronger than N–N single bond.
(iii) Ka2 << Ka1, because HSO -4 ion has much less tendency to donate a proton to H2O as
compared to H2SO4.
30. (a) Let the rate law be, r1 = k [A]2
(i) If [A] is doubled than rate r2 = k(2A)2 = 4k [A]2 = 4r1, i.e., rate becomes 4 times.
2
A 1 1 1
(ii) If [A] is reduced to half then rate, r 3 = k é ù = k [ A ] 2 = r1 , i.e., rate becomes
êë 2 úû 4 4 4
times
(b) For a first order reaction
2.303 [R] o
t= log
k [R]
Here, t = 3 h = 3 × 60 min = 180 min
k = 0.0051min–1, [R]o = 0.10 M, [R] = ?
2.303 0.10
180 min = log
-1 [R]
0.0051min
2.303 ´ R ´ T1 ´ T2 k
Ea = log 2
T2 – T1 k1
Fe 2+ ( aq) ¾® Fe 3 + ( aq) + e – ] ´ 5
¾
17. (i) Cationic Detergents: Cationic detergents are quaternary ammonium salts of amines with
acetates, chlorides or bromides as anions. Cationic part possess a long hydrocarbon chain and a
positive charge on nitrogen atom. Hence, these are called cationic detergents. Cetyltrimethylammonium
bromide is a popular cationic detergent and is used in hair conditioners.
+
é CH3 ù
ê ½ ú
êCH (CH ) ¾ N ¾ CH ú Br -
ê 3 2 15
½
3
ú
ê ú
êë CH3 úû
Cetyltrimethyl ammonium bromide
Cationic detergents have germicidal properties and are expensive, therefore, these are of
limited use.
Examination Papers | 111
(ii) Food Preservatives: These are the chemical substances which are added to the food materials
to prevent their spoilage due to microbial growth and to retain their nutritive value for long
periods.
Preservatives prevent the rancidity of food and inhibit growth or kill the microorganisms.
The most-common preservations used are, sugar table salt, sodium benzoate, Sodium
metabisulphite sorbic acid and propanoic acid.
19. d = 7.87 g cm–3, For bcc, Z = 2, M = 56 g mol–1
a = 286.65pm = 286.65 × 10–10cm, NA = ?
Z´ M
d=
a 3 ´ NA
2 ´ 56 g mol -1
7.87g cm–3 =
(286.65 ´ 10 -3 cm) 3 ´ NA
2 ´ 56 g mol -1
NA =
(2.8665 ´ 10 -8 cm) 3 ´ 7.87 g cm -3
2 ´ 56 g mol -1
=
23.553 ´ 10 -24 cm 3 ´ 7.87 g cm -3
112 mol -1
= = 0.604 × 1024 mol–1
-24
185.366 ´ 10
= 6.024 × 1023 mol–1.
22. (i) Chemisorption is caused by chemical bond formation where as physisorption arises due to Van
der Waals’ forces.
(ii) Chemisorption is highly specific in nature whereas physisorption is not specific.
(iii) Chemisorption results into unimolecular layer whereas physisorption results into
multimolecular layers.
(iv) Chemisorption is irreversible in nature whereas physisorption is reversible in nature.
(v) Chemisorption first increases with increase in temperature, then decreases while physisorption
decreases with increase in temperature.
24.
(i) Orbitals of Cr3+ ion
3d 4s 4p
[A ] -
log = -0.4768 = 1.5232
[A ]0
[A ] -
= Anti log 1.5232 = 0.3336
[A ]0
[A ]
= 0.334
[A ]0
OR
2.303 [A ]0
(i) t = log
k [A ]
[ A ] 0 100
Given: k = 1.06 ´ 10 -3 min -1 , =
[A ] 85
2.303 100 2303
t= log = [ 2 log10 - log 85] min
-3 -1 85 1.06
1.06 ´ 10 min
2303 2303 ´ 0.0706
t= [ 2 ´ 1 -1.9294] = = 153.39 min
1.06 1.06
t =153.4 min.
[ A ] 0 100
(ii) Given: k = 1.06 × 10–3 mm–1, =
[A ] 15
2.303 100 2303
t= , log = [ 2 log10 - log15] min
-3 -1 15 1.06
1.06 ´ 10 min
2303 2303 ´ 0.8239
= [ 2 ´ 1 -11761
. ]= min
1.06 1.06
t =1790 min.
330 - 350K
Ni + 4CO ¾ ¾ ¾ ¾
¾® Ni(CO) 4
impure Tetracarbonyl nickel (volatile)
450 - 470K
Ni(CO) 4 ¾ ¾ ¾ ¾
¾® Ni + 4CO
Pure
b.p. = 4
12. (i) No. of electron pairs around central atom (Xe) = 6 F F
l.p. = 2
The shape would be square planar. Xe
F F
O O
½½ ½½
(ii) S S
O
O O
OH OH
H2 S 2 O7 (Pyrosulphuric acid)
16.
Fat soluble vitamins Sources Deficiency diseases
Vitamin A Fish liver oil, carrots, milk Xerophthalmia, Night blindness.
Vitamin D Exposure to sunlight, fish and egg. Rickets and osteomalacia.
Vitamin E Vegetable oils like wheat germ oil, Sterility and muscular atrophy
sunflower oil, etc.
Vitamin K Green leafy vegetables Haemorrhages and increased blood
clotting time.
18. (i) Nucleotides: The monomeric unit of nucleic acid is called nucleotide. When a nucleoside is
linked to phosphoric acid at 5’ position of sugar moiety, we get nucleotide.
(ii) Nucleoside: A nucleoside is the condensation product of purine or pyrimidine base with
pentose sugar.
O
5¢ 5¢
HO—H2C Base O—P—O—H2C Base
4¢H H1¢ O– 4¢H H1¢
3¢ 2¢
H H H 3¢ 2¢
H
OH OH OH OH
Nucleoside Nucleotide
24. (i) Linkage isomerism: The isomers which have same molecular formula but differ in the linkage
of ligand atom to the central metal atom are called linkage isomers, e.g.,
[Co(NH3 ) 5 NO2 ]Cl 2 and [Co(NH3)5ONO]Cl2
Pentaamminenitrito–N–Cobalt (III) chloride pentaamminenitrito–O–Cobalt (III) chloride
Examination Papers | 115
(ii) Outer orbital complex: When ns, np and nd orbitals are involved in hybridisation, outer
orbital complex is formed, e.g., [CoF6 ] 2- in which cobalt is sp 3 d 2 hybridised.
(iii) Bidentate ligand: When a ligand is bound to a metal ion through two donor atoms it is said to be
&& — CH — CH — NH
bidentate ligand, e.g., H2 N && 2-
2 2 2 (ethane–1, 2–diamine, C 2 O 4 (oxalate), etc.
General Instructions:
(i) All questions are compulsory.
(ii) Question nos. 1 to 8 are very short answer questions and carry 1 mark each.
(iii) Question nos. 9 to 18 are short answer questions and carry 2 marks each.
(iv) Question nos. 19 to 27 are also short answer questions and carry 3 marks each.
(v) Question nos. 28 to 30 are long answer questions and carry 5 marks each.
(vi) Use log tables if necessary, use of calculators is not allowed.
14. Name the following coordination compounds according to IUPAC system of nomenclature:
(i) [Co(NH3)4 (H2O) Cl]Cl2
(ii) [CrCl2(en)2]Cl, (en = ethane –1, 2 – diamine)
15. Illustrate the following reactions giving a chemical equation for each:
(i) Kolbe's reaction, (ii) Williamson synthesis.
16. How are the following conversions carried out?
(i) Benzyl chloride to benzyl alcohol,
(ii) Methyl magnesium bromide to 2-methylpropan-2-ol.
17. Explain the following terms:
(i) Invert sugar (ii) Polypeptides
OR
Name the products of hydrolysis of sucrose. Why is sucrose not a reducing sugar?
18. What are essential and non-essential amino acids in human food? Give one example of each type.
19. The well known mineral fluorite is chemically calcium fluoride. It is known that in one unit cell of this
mineral there are 4 Ca2+ ions and 8 F– ions and that Ca2+ ions are arranged in a fcc lattice. The F– ions
fill all the tetrahedral holes in the face centred cubic lattice of Ca2+ ions. The edge of the unit cell is
5.46 × 10–8 cm in length. The density of the solid is 3.18 g cm–3. Use this information to calculate
Avogadro's number (Molar mass of CaF2 = 78.08 g mol–1)
20. A solution prepared by dissolving 1.25 g of oil of winter green (methyl salicylate) in 99.0 g of benzene
has a boiling point of 80.31°C. Determine the molar mass of this compound. (B.P. of pure Benzene =
80.10°C and Kb for benzene = 2.53°C kg mol–1)
21. What is the difference between multimolecular and macromolecular colloids? Give one example of
each type. How are associated colloids different from these two types of colloids?
22. Describe how the following changes are brought about:
(i) Pig iron into steel.
(ii) Zinc oxide into metallic zinc.
(iii) Impure titanium into pure titanium.
OR
Describe the role of
(i) NaCN in the extraction of gold from gold ore.
(ii) SiO2 in the extraction of copper from copper matte
(iii) Iodine in the refining of Zirconium
Write chemical equations for the involved reactions.
23. How would you account for the following?
(i) The atomic radii of the metals of the third (5d) series of transition elements are virtually the
same as those of the corresponding members of the second (4d) series.
118 Xam idea Chemistry—XII
(ii) The E° value for the Mn 3 + / Mn 2 + couple is much more positive than that for Cr 3 + / Cr 2 +
couple or Fe 3 + / Fe 2 + couple.
(iii) The highest oxidation state of a metal is exhibited in its oxide or fluoride.
24. (i) State one use each of DDT and iodoform.
(ii) Which compound in the following couples will react faster in S N 2 displacement and why?
(a) 1-Bromopentane or 2-bromopentane
(b) 1-Bromo-2-methylbutane or 2-bromo-2-methylbutane.
25. In the following cases rearrange the compounds as directed:
(i) In an increasing order of basic strength:
C 6 H5 NH2 , C 6 H5 N(CH3 ) 2 , (C 2 H5 ) 2 NH and CH3 NH2
(ii) In a decreasing order of basic strength:
Aniline, p-nitroaniline and p-toluidine
(iii) In an increasing order of pKb values:
C 2 H5 NH2 , C 6 H5 NHCH3 , ( C 2 H5 ) 2 NH and C 6 H5 NH2
26. Give one example each of
(i) addition polymers, (ii) condensation polymers,
(iii) copolymers.
27. What are analgesic medicines? How are they classified and when are they commonly recommended
for use?
28. (a) State Kohlrausch law of independent migration of ions. Write an expression for the molar
conductivity of acetic acid at infinite dilution according to Kohlrausch law.
(b) Calculate L°m for acetic acid.
(ii) XeF4 + H2 O ¾
¾®
(b) Explain the following observations giving appropriate reasons:
(i) The stability of +5 oxidation state decreases down the group in group 15 of the periodic table.
(ii) Solid phosphorus pentachloride behaves as an ionic compound.
(iii) Halogens are strong oxidizing agents.
30. (a) Explain the mechanism of a nucleophilic attack on the carbonyl group of an aldehyde or a ketone.
(b) An organic compound (A) (molecular formula C8 H16 O2 ) was hydrolysed with dilute
sulphuric acid to give a carboxylic acid (B) and an alcohol (C). Oxidation of (C) with chromic
acid also produced (B). On dehydration (C) gives but-1-ene. Write the equations for the
reactions involved.
OR
(a) Give chemical tests to distinguish between the following pairs of compounds:
(i) Ethanal and propanal
(ii) Phenol and Benzoic acid
(b) How will you bring about the following conversions?
(i) Benzoic acid to benzaldehyde
(ii) Ethanal to but-2-enal
(iii) Propanone to propene
Give complete reaction in each case.
20. How are the following colloids different from each other in respect of their dispersion medium and
dispersed phase? Give one example of each.
(i) Aerosol (ii) Emulsion
(iii) Hydrosol
26. Differentiate between thermoplastic and thermosetting polymers. Give one example of each.
27. Explain the following terms with one suitable example in each case.
(i) Cationic detergents (ii) Enzymes
(iii) Antifertility drugs
Solutions
CBSE (Delhi) SET–I
1. Metals are malleable and ductile whereas ionic solids are hard and brittle.
2. The order of a reaction can be defined as the sum of the powers of the concentration terms as
expressed in rate law.
3. An emulsion is a colloidal dispersion of one liquid in another liquid. For example, cod liver oil, milk
etc.
4. The dimerisation of NO2 is because of unpaired electron on nitrogen atom to form N2O4 molecule
with even number of electrons.
l
262 K
2NO2 N2 O4
Paramagnetic Colourless and diamagnetic
7. CH3 — CH2 — C —
8. But-3-en-1-amine.
9. When the vapour pressure of a solution is either higher or lower than that predicted by Raoult’s law
then the solution exhibits deviation from Raoult’s law.
These deviation are caused when solute-solvent molecular interactions ( A - B) are either weak or
stronger than solvent-solvent ( A - A) or solute-solute ( B - B) molecular interactions.
Positive Deviation: When ( A - B) molecular interactions are weaker than ( A - A) and ( B - B)
molecular interactions. For example a mixture of ethanol and acetone.
Negative deviation: When ( A - B) molecular interactions are stronger than ( A - A) and ( B - B)
molecular interactions. For example a mixture of chloroform and acetone.
122 Xam idea Chemistry—XII
Cl
H3C
C O H C Cl
H3C
Cl
Hydrogen bond
13. (i) The density of elements from titanium to copper increase in the first series of transition
elements. This is due to decrease in metallic radius coupled with increase in atomic mass
results in a general increase in the density.
(ii) Many transition metals and their components show catalytic properties. This property is due to
their ability to exhibit variable oxidation states (incomplete d-orbitals) which enable them to
form unstable intermediates.
14. (i) Tetraammineaquachloridocobalt (III) chloride
(ii) Dichlorido-bis (ethane-1, 2-diamine) chromium(III)chloride
Examination Papers 123
16. (i)
CH2 Cl CH2 OH
½ ½
KOH (aq), heat
¾¾¾¾®
– KCl
17. (i) Invert Sugar: The dextrorotatory sucrose when hydrolysed by boiling with mineral acid
produces an equal number of molecules of dextrorotatory fructose. The resulting mixture is
laevorotatory and termed as invert sugar.
H+
C12 H22 OH + H2O ¾ ¾ ¾® C6H12O6 + C6H12O6
Sucrose Glucose Fructose
[a]D = 66.5° [a]D = 52.5° [a]D = – 93°
Invert sugar
(ii) Polypeptides: Polypeptides are polymers formed by condensation of more than ten amino
acids. They have large number of peptides bonds in them. Polypeptides are amphoteric
because of the presence of terminal-ammonium and carboxylate ions as well as the ionized
side chains of amino acid residues
OR
Sucrose gives glucose and fructose on hydrolysis. It is a non-reducing sugar as it does not contain
free ketone or aldehyde group in its ring form.
124 Xam idea Chemistry—XII
18. Essential amino acids: Amino acids which cannot be synthesized in the body but must be obtained
through diet, are called essential amino acids. For example: valine, leucine.
Non-essential amino acids: The amino acids, which can be synthesized in the body are known as
non-essential amino acids. For example: Glycine, Alanine.
19. Given: d = 3.18 g cm–3, Z = 4, a = 5.46 × 10–8 cm
M = 78.08 g mol–1 NA = ?
Z´M
d=
a3 ´ NA
Z´M
\ NA =
a3 ´ P
Substituting the given values, we get
4 ´ 78.08
NA =
(5.46 ´ 10 -8 ) -3 ´ 318
.
313 × 32 ´ 10 24
NA =
517 × 61
NA = 6.035 × 1023 mol -1
20. Given DTB = 80.31 – 80.10 = 0.21 °C or 0.21 K
WB = 1.25g, Kb = 2.53°C kg mol–1
MB = ?
WA = 99g
K ´ WB
MB = b ´ 1000
DTb ´ WA
2 × 53 ´ 1× 25 ´ 1000 3162.5
= =
0 × 21´ 99 20.79
\ MB = 152 g/mol
21. Multimolecular colloids: In this type of colloids, colloidal particles are aggregates of atoms or
molecules each having size less than 1nm, e.g., sulphur sol, gold sol.
Macromolecular colloids: In this type of colloids, colloidal particles are themselves large molecules
of colloidal dimensions, e.g., starch, proteins, polyethene, etc.
Associated colloids: There are certain substances which at low concentrations behave as normal
electrolyte, but at higher concentrations exhibit colloidal behaviour due to the formation of
aggregates. Such colloids are known as associated colloids, e.g., soaps and detergents.
22. (i) Pig iron into steel: Pig iron is converted into steel by heating in a converter. A blast of oxygen
diluted with carbon dioxide is blown through the converter. Oxygen reacts with impurities and
raised the temperature to 2173K. Carbon gets oxidised to CO which burns off at the mouth of
the converter. Oxides of silicon and Mg form slag. When the flame is stopped, slag is tapped
off and other metals like Mn, Cr, Ni, W may be added in the end.
(ii) Metallic zinc can be obtained from zinc oxide. At first calcination of ZnO is done and
converted into sinters of oxide.
Examination Papers 125
D
ZnO + C ¾¾® Zn + CO
The oxide is then made into brickettes with coke and clay and heated by producer gas in
vertical retorts at 1673 K, zinc, boiling point is 1183 K, distills off and is collected by rapid
chilling.
(iii) Impure Titanium into pure Titanium: Impure Titanium is heated with I2 to form volatile
complex (TiI4), which on heating at higher temperature decomposes to give pure titanium.
D
Ti (impure) + 2 I2 ¾® TiI4
¾¾ ¾ ¾¾® Ti (pure) + I2
OR
(i) Role of NaCN in the extraction of gold is to do the leaching of gold ore in the presence of air
from which the gold is obtained later by replacement.
4Au(s) + 8NaCN(aq) + 2H2O + O2 ¾
¾® 4Na[Au(CN)2] + 4KOH
(ii) SiO2 is added to copper matte to convert the leftout FeS, FeO into slag.
FeO + SiO2 ¾¾® FeSiO3 (Slag)
(iii) Iodine is heated with impure Zr to form volatile compound which on further heating
decomposes to give pure zirconium.
D D
Zr (Impure) + I2 ¾ ¾¾® ZrI4 ¾ ¾¾® Zr (pure) + 2I2
27. Analgesics: They are the drugs used for relieving pain. Analgesics are classified into two categories:
(a) Narcotics (addictive) drugs (b) Non-narcotics (non-addictive) drugs
(a) Narcotics: Narcotic drugs are recommended for cardiac pain, post operative pains, terminal
cancer and in child birth.
(b) Non-narcotics: Non-narcotic drugs are effective in relieving skeletal pain, reducing fever,
preventing heart attack.
28. (a) Kohlrausch Law: “The molar conductance of an electrolyte at infinite dilution is equal to the
sum of the molar conductances of the two ions, i.e., the cation and the anion.”
Mathematically, Lom = Lo+ + Lo-
Expression for the molar conductivity of acetic acid:
Lom CH3 COOH = Lom CH3 COO- + Lo
H+
intermediate is produced. The intermediate captures a proton from the medium to give the
neutral product.
Nu Nu
l lfast
d+ d– slow – H
+
C O + Nu C O C O H
step-1
Aldehyde or ketone Tetrahedral step-2 Addition product
(Planar) intermediate
(b) The hydrolysis of the given compound with dil H2SO4 to give a carboxylic acid and an alcohol
suggests that the compound is an ester.
O O
|| ||
dil. H SO4
R — C— OR' ¾ ¾ ¾2 ¾ ¾® R — C— OH + R — OH
( B) ( C)
So, the possible structure of ‘A’ is
O
||
CH3 — CH2 — CH2 — C— O — CH2 CH2 CH2 CH3
Butyl butanoate
O
||
(i) CH3 — CH2 — CH2 — C— O — CH2 CH2 CH2 CH3
(A) dil. H SO
¾ ¾ ¾2 ¾
¾4
® CH3 CH2 CH2 COOH + CH3 CH2 CH2 CH2 OH
Butanoic acid Butanol
(B) (C)
chromic acid
(ii) CH3 CH2 CH2 CH2 OH ¾ ¾ ¾ ¾¾® CH3 CH2 CH2 COOH
Butanol oxidation Butanoic acid
(C) (B)
3– +
6 + FeCl3 [Fe(OC6H5)6] + 3H + HCl
Violet complex
Phenol
Examination Papers 129
LiAlH4 P.C.C
(i)
Br F
Bent T-shaped
(ii) Structure of XeF4 molecule
F F
Xe
F F
Square planar
130 Xam idea Chemistry—XII
14. Co 3+
l
l
(i) \
3d6 4s 4p
\ Co 3+
l
l
l
3d 4s 4p
2 3
d sp hybridization
Thus, the complex will be octahedral and diamagnetic.
(ii) [Ni(CN)4] 2-
The electronic configuration of the nickel atom and Ni 2+ ion are depicted below:
l
3d2 4s2 4p0
\ Ni 2+ (after rearrangement)
l
l
l
l
dsp2 hybridization
The resulting complex is square planar and diamagnetic as it has no unpaired electrons.
15. (i) Reimer Tiemann Reaction
OH é ONa ù ONa OH
ê ½ ú
½ ê CHCl 2ú ½ ½
CHO + CHO
CHCl 3 (aq.) NaOH ê ú NaOH H 3O
¾¾¾¾¾® ê ú ¾¾® ¾®
340 K ê ú
ê ú
Salicyladehyde
ê ú (2-Hydroxy benzaldehyde)
êë úû
(ii) Friedel - Craft Reactions
Acylation:
O
||
C— CH3
O ½
||
Anhyd. AlCl
+ CH3 — C— Cl ¾ ¾ ¾ ¾¾3 ® + HCl
Benzene Acetophenone
Examination Papers 131
Alkylation:
CH3
½
Anhyd. AlCl
+ CH3 Cl ¾ ¾ ¾ ¾¾3 ® + HCl
Methyl
chloride
Benzene Toluene
16. OH
|
dil. H SO4
(i) CH3 — CH CH2 ¾ ¾ ¾2 ¾ ¾® CH3 — CH — CH3
Propene Propane-2-ol
( i ) HCHO
(ii) C 2 H5 MgCl ¾ ¾ ¾ ¾® CH3 — CH2 — CH2 OH
Ethyl magnesium chloride (ii) H + Propan -1-ol
¾ N = N¾ ¾ NH2 + HCl
p -Amino azobenzene
+ (yellow dye)
(ii) Ar N2 Cl - + CH3 ¾ CH2 ¾ OH ¾® ArH + N2 + CH3 ¾ CHO + HCl
D
(iii) R ¾ NH2 + CHCl 3 + 3KOH (alc.) ¾¾¾® R ¾ NC + 3KCl + 3H2 O
1° amine Alkyl isocyanide
132 Xam idea Chemistry—XII
O
7.8
pm
116.8°
O O O O O
O
General Instructions:
(i) All questions are compulsory.
(ii) Question nos. 1 to 8 are very short answer questions and carry 1 mark each.
(iii) Question nos. 9 to 18 are short answer questions and carry 2 marks each.
(iv) Question nos. 19 to 27 are also short answer questions and carry 3 marks each.
(v) Question nos. 28 to 30 are long answer questions and carry 5 marks each.
(vi) Use log tables if necessary, use of calculators is not allowed.
(b) The rate of a reaction increases four times when the temperature changes from 300 K to 320 K.
Calculate the energy of activation of reaction, assuming that it does not change with
temperature. (R = 8.314 J K–1 mol–1)
29. (a) Complete the following chemical equations:
(i) Cr2 O72– (aq) + H2S(g) + H+(aq) ¾¾®
Solutions
CBSE (All India) SET–I
1. The interactions hold the molecules together in a polar molecular solid is dipole-dipole attractions.
2. When concentration of an electrolyte approaches zero, the molar conductivity is known as limiting
molar conductivity (Lom ).
3. Fluorine does not exhibit any positive oxidation state because it is the most electronegative element in
the periodic table.
4. 4–Bromo–3–methyl–pent–2–ene
5.
OH
CH2 CH CH3
6. Tollen’s reagent – A solution of AgNO3 dissolved in NH4OH is known as Tollen’s reagent. This is
used to detect the presence of –CHO group in an organic compound. For example:
RCHO + 2Ag (NH3)2 OH ¾¾® RCOONH4 + 2Ag¯ + H2O + 3NH3.
7. Reducing Sugars: The carbohydrates which reduces Fehling’s Reagent and Tollen’s Reagent are
referred to as reducing sugar. For example, all monosaccharide are reducing sugars.
8. Each monomer of nylon 6, 6 consists of six carbon each.
9. Osmosis: The phenomenon in which solvent molecules flow through a semipermeable membrane
from a solution of low concentration to a solution of higher concentration is termed as osmosis.
140 Xam idea Chemistry—XII
Osmotic Pressure: The hydrostatic pressure exerted by the column of the solution which is just
sufficient to prevent the osmosis is called osmotic pressure.
Advantage of using osmotic pressure as compared to other collegative properties:
(i) The equilibrium is established very quickly. Hence, results are obtained in a very short time.
(ii) The concentration of the solution does not change during determination of osmotic pressure.
(iii) This is ideal method for proteins to find their molar mass since it happens at room temperature
and no coagulation occurs.
10. Conductivity (K) = 1
× Cell constant
Resistance ( R)
Conductivity ( k) ´ 1000
Molar Conductivity ( L m ) =
Molarity ( M )
OR
K ´1000 L m ´ M
Lm = =
M 1000
138.95 cm 2 mol –1 ´ 1.5 mol L–1
K = = 0.208355 cm–1
3 –1
1000 cm L
11. Increasing order of reducing power:
Ag < Cu < Fe < Cr < Mg < K
OR
(i) MnO-4 + 8H+ + Se ¾¾® Mn2+ + 4H2O, DE° = + 1.51V (Reduction)
E °cell = E °R - E °L
= 1.51 – 0.15 = 1.36 V
Since E °cell is positive, therefore it will favour product formation.
12. (i) Tyndall effect: Tyndall (1869) observed that when a beam of light is passed through a
colloidal solution whose particle size is comparable to the wave length of light, the path of the
beam is illuminated. This phenomenon is called Tyndall effect.
(ii) Shape Selective Catalyst: The catalysis reaction which depends upon the pore size of the
catalyst and the size of the reactant and product molecules is called shape-selective catalysis.
Zeolites are good shape-selective catalysts because of their honey comb-like structures. ZSM-5
used in petroleum industry to convert alcohols directly into gasoline by dehydrating them to
give a mixture of hydrocarbons.
ZSM -5
x CH3 — OH ¾ ¾¾
¾® (CH2 ) x + xH2 O
Gasoline
Examination Papers 141
13. The colloidal particles bear similar electric charge and that is why they stay away from each other due
to repulsion. If the charge is removed, they come together and are precipitated.
The precipitation and settling down of the discharged particles is called coagulation or flocculation.
The coagulation of a lyophobic sols can be done by mixing of two opposite charged sols or by
addition of electrolyte.
14. (i) I2 + 10HNO3 ¾¾® 2HIO3 + 10NO2 + 4H2O
(ii) 3HgCl2 + 2PH3 ¾¾® Hg3P2 + 6HCl
15. (i) (ii)
O O
|| || F F
P P
H O H Xe
OH OH
H4P2O5 F F
Xe F4 (Square planar)
16. (i) To distinguish Ethylamine and aniline.
Chemical Test C2H5NH2 C6H5NH2
Azo dye Test: No reaction Yellow orange dye is obtained.
+ –
Add NaNO2 + dil. HCl at 273 - 278K NH2 N –– N–Cl
followed by NaOH and b-naphthol | |
NaNO 2/HCl
+ 2H2O
273–278
+ –
N––
– NCl
|
(i) HONO
+ N2 +HCl
(ii) H2O
+ -
(ii) C 6 H5 NH2 ¾NaNO 2 /HCl C6H5 NH 2 NH2
¾¾¾¾ ® C 6 H5 N º N Cl ¾ ¾¾¾ ¾® C 6 H5 N = N
OH –
Benzene
p-Amino-azobenzene
diazonium chloride
(B)
(A)
21. (i) NaCN is used in the leaching of argentite (Ag2S). Argentite is leached with dilute aqueous
solution of NaCN in the presence of air
Ag2S + 4NaCN ¾¾® 2 Na [Ag (CN)2] + Na2S.
(ii) Iodine in the refining of titanium.
The crude metal is heated with iodine in an evacuated vessel to form volatile compound.
Ti (impure) + 2I2 ¾¾® TiI4
Metal iodide decomposes on heating at 1800°C on a tungston filament. The pure metal deposit
on the filament.
1800 °C
TiI 4 ¾ ¾¾
¾® Ti(pure) + 2I 2
(iii) Cryolite in the metallurgy of aluminium: In the metallurgy of Al, purified Al2O3 is mixed
with cryolite (Na3AlF6) which lowers the melting point of the mixture and increase the
conductivity.
OR
(i) Froth floatation method: This method is used to remove gangue from sulphide ores. In this
process a suspension of the powdered ore is made with water, some pine oil (collector) and
stablisers are added. A rotating paddle agitates the mixture and draws air in it. The froth is light
and it skimmed off.
(ii) Electro refining of metals: In this method, the impure metal is made to act as anode. A strip of
the same metal in pure form is used a cathode. They are put in a suitable electrolyte containing
soluble salt of the same metal.
Anode: M ¾¾® M n + + ne –
23. SN1 Reactions: They are substitution nucleophilic unimolecular reactions in which the rate of
the reaction depends on the concentration of only one reactant. Product formation takes place
by the formation of carbo cation as reaction intermediate. For example:
CH 3 CH 3 CH 3 CH 3
–
Slow step OH
CH 3 C Br C+ CH 3 C OH
Fast
CH 3 CH 3 CH 3
SN2 reactions they are substitution nucleophilic bimolecular reactions in which rate of the
reaction depends on the concentration of two reactants. For example:
OH -
R — Cl ¾ ¾¾® R — OH + Cl -
Rate µ [R – Cl][OH– ]
The product formation takes place by formation of transition state.
24. (i)
OH O
K2Cr2O7/H2SO4
O
Phenol p-Benzoquinone
(ii)
OMgCl OH
O
CH 3MgCl +
H 2O/H C CH 3
CH 3 C CH 3 CH 3 C CH 3 CH 3
Propanone
CH 3 CH 3
2-Methyl propan-2-ol
OH
dil H2SO 4
(iii) CH3— CH CH2 CH 3—CH—CH 3
Propene Propan-2-ol
25. (i) This is because of (a) bond dissociation enthalpy of F2 is lower than Cl2 and (b) fluorine forms
stronger bond with nitrogen due to comparable size.
(ii) As xenon is sp3 hybridised with three lone pair of electrons.
(iii) This is due to (a) low bond dissociation enthalpy of F2 and (b) high hydration enthalpy of F - .
26. This is due to presence of carboxylic acid as well as amino groups.
O
l Amino acids which contain two —C—O—H group and one —NH2 group are called acidic amino
acid, e.g., aspartic acid.
Examination Papers 145
O
l Amino acids which contain two —NH2 group and one —C—O—H group are called basic amino
acids, e.g., lysine.
O
l Amino acids which contain one —C—O—H and one —NH2 group are called neutral amino
acids, e.g., glycine.
l Amino acids that cannot be synthesized by the body and must be supplied in the diet are called
essential amino acids, e.g., lysine, valine, leucine, etc.
l The amino acids which are synthesized by our body are called non-essential amino acids, e.g.,
alanine, glycine, etc.
27. (i) Food preservatives: Chemical substance which are used to prevent food spoilage due to
microbial growth are called preservative. For example, sodium benzoate, potassium sorbate,
etc.
(ii) Enzymes: Enzymes are the essential biological catalysts which catalyse specific biological
reactions at a very high rate under mild conditions of temperature and pH. For example,
invertase, zymase etc.
(iii) Detergents: They are very similar to the salts of fatty acids found in soap but they are
manufactured from materials other than animal fats. For example: Sodium alkylbenzene
sulphonates are common ingredients of synthetic detergents.
28. (a) (i) Rate of Reaction: It is defined as the decrease in the concentration of reactants per unit time
or increase in the concentration of products per unit time.
For a hypothetical reaction R ® P
– D[R] +D [P]
Rate = Rate =
Dt Dt
(ii) Activation energy: The amount of energy which the reactants must absorb to pass over the
energy barrier between reactants and products is known as the activation energy.
2.303 [A ]o
(b) (i) We know that k = log
t [A ]t
0.693
t1/2 =
k
0.693
\ k=
t1/ 2
0.693
\ k=
37.9
\ k = 0.0183 s–1
2.303 [A] o
k= log
t [A]
2 . 303 1
\ t= log
0 . 0183 14
2.303 2 ´ 2.303
= log 2 2 = log 2
0.0183 0 . 0183
146 Xam idea Chemistry—XII
2 ´ 2.303
t= × 0.3010
0.0183
t = 75.8 s.
(ii) 1 minute = 60 second
2.303 [A] o
t= log
k [A]
2.303 [A] o
60 = ´ log
0.0183 [A]
60 ´ 0 . 0183 [A] o
= log
2 . 303 [A]
Taking antilog,
[A] o
0.4767 = log
[A]
[A] o
Antilog (0.4767) =
[A]
[A] o
2.997 =
[A]
[A] 1
= = 0.333 = 0.333%
[A] o 2 . 997
Hence, amount left out = 33.3%
OR
(a) (i) The order of a reaction can be defined as the sum of the powers of the concentration
terms as expressed in rate law.
(ii) Molecularity: It may be defined as the number of reacting species (molecules, atoms or
ions) taking part in an elementary reaction, which must collide simultaneously in order to
bring about a chemical reaction.
(b) (i) Given T1 = 300 K
T2 = 320 K
R = 8.134 JK–1 mol–1
Ea = ?
é TT ù k
We know that, Ea = 2.303 R ê 1 2 ú log 2
ë T2 - T1 û k1
é300 ´ 320 ù
Ea = 2.303 × 8.314 ê ú log 4
ë 20 û
Ea = 19.15 [4800] × 0.602
= 55.32 kJ mol–1.
29. (a) (i) Cr2O72– + 3H2S + 8H+ ¾¾® 2Cr3+ + 3S + 7H2O
(ii) 2Cu2+ + 4I –
¾¾® Cu2I2 + I2
Examination Papers 147
(b) (i) The oxidising power of oxonions are in the order VO2+ < Cr2 O72– < MnO4–, this is due
to increase in the oxidation state of the metal ion.
(ii) The third ionisation enthalpy of manganese (Z = 25) is exceptionally high because Mn2+
ion has 3d5 configuration which is highly stable since it is half-filled.
(iii) Cr2+ stronger reducing agent than Fe2+ as its configuration changes from d4 to d3, a more
stable half filled t2g configuration.
OR
(a) (i) 8Mn O-4 (aq) + 3S 2 O23 - (aq) + H2 O ¾¾® 8MnO2 + 6SO24 - + 2OH-
(ii) Cr2 O7 (aq) + 6Fe 2 + (aq) + 14H+ ¾¾® 2Cr 3 + + 6Fe 3 + + 7H2 O.
(b) (i) La3+ and Lu3+ ions do not show any colour in solution because they do not contain any
unpaired electrons.
(ii) Among the divalent cations in the first series of transition elements, manganese exhibits
the maximum paramagnetism because manganese (Mn2+) ion has maximum number of 5
unpaired electrons.
(iii) Cu+ ion is not known in aqueous solutions because Cu2+ ions are more stable due to more
negative DHhyd of Cu2+ than Cu+, which compensates for the second ionisation enthalpy
of Cu.
30. (a) (i) Clemmensen reaction
O
CH 3—C—CH 3 Zn–Hg/HCl (conc.) CH 3—CH 2—CH 3
Acetone Propane
C 2H 5 COOH
–
KMnO4/OH
(ii)
Br CN COOH
CuCN H2O/H +
(iii) Py,473K
OR
(a) (i) Hell-Volhard-Zelinsky reaction
(i) X 2 /red P
R—CH2—COOH ¾ ¾¾¾¾ ® R—CH—COOH ( X == Cl, Br)
(ii) H 2 O |
X
Carboxylic acid a -Halocarboxylic acid
(ii) Wolf-Kishner reduction
2 2 (i) NH - NH
CH3 COCH 3 ¾ ¾¾¾¾¾¾¾¾® CH3 CH2 CH3
(ii) KOH, Ethylene glycol, D Propane
Propanone
CH 3 COOH
–
(i) KMnO4/OH
(iii)
(ii) H +
Methyl benzene Benzoic acid
Dimethyl amine forms nitroso amine which is water insoluble yellow oil.
(CH3 ) 2 NH + HONO ¾¾® (CH3 ) 2 N – N = O + H2 O
N-Nitroso
dimethyl amine
(yellow oil)
(iii) Aniline and N-methyl aniline
Test: Carbyl amine test:
Aniline on warming with chloroform and KOH gives offensive smell of carbylamine while
N-methyl aniline does not.
C 6 H5 NH2 + CHCl 3 + 3KOH ¾¾® C 6 H5 NC + 3KCl + 3H2 O
Aniline Phenyl
carbylamine
18. (i) Bakelite
Monomers: Phenol and formaldehyde
Structure:
OH
O
and H—C—H
Phenol Formaldehyde
(ii) Nylon–6
Monomers: Caprolactum
H
½
N
H2 C C=O
½ ½
H2 C CH2
H2 C ¾ CH2
Caprolactum
19. Atomic mass (M) = 108 g mol–1, a = 409 pm
We know that for fcc lattice:
a
r=
2 2
409 409
\ r= =
2 ´ 1.414 2.828
r = 144.62 pm
–1
20. MB = 62.0 g mol , WA = 5.50 kg or 5500 g
Kf = 1.86 K kg mol–1, D Tf = 10 K
150 Xam idea Chemistry—XII
We know that,
WB 1000
D Tf = Kf × ´
M B WA
WB 1000
10 = 1.86 × ´
62 5500
62 ´ 5500 ´ 10
WB =
1000 ´ 186
.
3410000
\ WB = = 1833.3 g
1860
27. Analgesics: They are the drugs used for relieving pain. Analgesics are classified into two categories:
(a) Narcotics (addictive) drugs (b) Non-narcotics (non-addictive) drugs
(a) Narcotics: Narcotic drugs are recommended for cardiac pain, post operative pains, terminal
cancer and in child birth.
(b) Non-narcotics: Non-narcotic drugs are effective in relieving skeletal pain, reducing fever,
preventing heart attack.
10 . 5 ´ 6 . 022 ´ 10 23 ´ ( 4 . 07 ´ 10 -8 ) 3
\ M=
4
M = 106.5 g mol–1
20. Given: WB = 15 g, WA = 450 g
D Tf = [273 – (273 – 0.34)]K = 0.34 K
MB = ?, Kf = 1.86 K kg mol–1
W ´ 1000
Þ MB = Kf × B
DTf ´ WA
15 g ´ 1000
= 1.86 K kg mol–1 × = 182.3 g mol–1
0.34 K ´ 450 kg
Examination Papers 151
22. (i) This is due to smaller size of oxygen the electron cloud is distributed over a small region of
space, making electron density high which repels the incoming electrons.
(ii) Because P—P bond is stronger than N—N bond.
(iii) Fluorine never acts as the central atom in polyatomic inter-halogen compounds since it is the
most electronegative element of the group.
25. (i) Tetrachloridocobaltate (II) ion
sp3 hybridisation
Tetrahedral
Paramagnetic
(ii) Tetracyanonickelate (II) ion
dsp2 hybridisation
Square plannar
Diamagnetic.
(iii) Diaquadioxalatochromate (III) ion
d2sp3 hybridisation
Octahedral
Paramagnetic.
26.
Fibrous Proteins Globular Proteins
1. Consist of linear thread-like molecules 1. Polypeptide chain is folded, around itself
which tend to lie side by side to form fibre forming almost spheroidal shape.
like structure.
2. Insoluble in water. 2. Soluble in water.
3. Keratin in hair, fibroin in silk, etc. 3. Albumin in eggs, insulin, etc.
Denaturation of Proteins
When a protein in its native form, is subjected to a change in temperature or change in pH, the hydrogen
bond are disturbed. Due to this, globules unfold and helix get uncoiled and protein loses its biological
activity. This is called denaturation of protein. During denaturation 2° and 3° structures are destroyed but
1° structures remain intact, e.g., coagulation of egg white on boiling, curdling of milk, etc.
27. (i) Antibiotics
The chemical substances produced from some micro-organism and are used to inhibit the
growth of other microorganism or even kill them are called antibiotics. For example, penicillin,
chloramphenicol.
(ii) Antiseptics
Antiseptics are the chemicals which prevent or destroy the growth of the harmful microorganism.
For example: Savlon, dettol.
(iii) Analgesics
These are the substances which are used to get relief from pain. For example: Aspirin.
CBSE EXAMINATION PAPERS
FOREIGN–2010
Time allowed : 3 hours] [Maximum marks : 70
General Instructions:
(i) All questions are compulsory.
(ii) Question nos. 1 to 8 are very short answer questions and carry 1 mark each.
(iii) Question nos. 9 to 18 are short answer questions and carry 2 marks each.
(iv) Question nos. 19 to 27 are also short answer questions and carry 3 marks each.
(v) Question nos. 28 to 30 are long answer questions and carry 5 marks each.
(vi) Use log tables if necessary, use of calculators is not allowed.
14. Describe the state of hybridization, the shape and the magnetic behaviour of the following complexes:
(i) [Cr(H2O)2(C2O4)2]–
(ii) [Co(NH3)2(en)2]3+, (en = ethane-1,2-diamine)
(At. Nos : Cr = 24, Co = 27)
OR
Explain the following terms:
(i) Crystal field splitting in an octahedral field
(ii) Spectrochemical series.
15. Write the mechanisms of the following reactions:
(i) Hydration of ethene to ethanol
(ii) Dehydration of ethanol, giving ethene.
16. Illustrate the following name reactions giving chemical equations:
(i) Reimer-Tiemann reaction
(ii) Williamson synthesis.
17. Explain the following giving a reason in each case:
(i) Why is an alkylamine more basic than ammonia?
(ii) Why do primary amines have higher boiling points than the tertiary amines?
18. Complete the following reaction equations:
(i) C6H5NH2 + CHCl 3 + KOH (alc) ¾
¾®
21. What is the difference between multimolecular and macromolecular colloids? Give one example of
each type. How are associated colloids different from the above two types of colloids?
22. Explain the following observations:
(i) The enthalpies of atomisation of transition metals are quite high.
(ii) There is a close similarity in physical and chemical properties of the 4 d and 5 d series of the
transition elements, much more than expected on the basis of usual family relationship.
(iii) The members in the actinoid series exhibit larger number of oxidation states than the
corresponding members in the lanthanoid series.
23. Answer the following:
(i) Identify chiral in CH3CHOHCH2CH3 and CH3CHOHCH3.
154 Xam idea Chemistry—XII
(ii) Among the following compounds, which one is more easily hydrolysed and why?
CH3CHCICH2CH3 or CH3CH2CH2CH2Cl
2
(iii) Which of these will react faster in SN displacement and why?
1-bromopentane or 2-bromopentane
24. Describe how the following changes are brought about:
(i) Pig iron into steel (ii) Bauxite into pure alumina
(iii) Impure copper into pure copper.
25. Explain the meanings of the following terms:
(i) Invert sugar (ii) Peptide linkage
(iii) Denaturation of proteins.
OR
Mention three such facts/reactions about glucose which cannot be explained by its open end structure.
What is meant by pyranose structure of glucose?
26. Identify the four groups into which the polymers are classified on the basis of the magnitude of
intermolecular forces present in them. To which group or groups do polythene and bakelite belong?
27. How do antiseptics differ from disinfectants? Name a substance that can be used as an antiseptic as
well as a disinfectant.
28. (a) Non-ideal solutions exhibit either positive or negative deviations from Raoult's law. What are
these deviations and how are they caused?
(b) What mass of NaCl (molar mass = 58.5 g mol–1) must be dissolved in 65g of water to lower
the freezing point by 7.50°C? The freezing point depression constant, Kf for water is 1.86 K kg
mol–1. Assume van't Hoff factor for NaCl is 1.87.
OR
(a) Define the terms osmosis and osmotic pressure. What is the advantage of using osmotic
pressure as compared to other colligative properties for the determination of molar masses of
solutes in solution?
(b) A solution prepared from 1.25 g of oil of wintergreen (methyl salicylate) in 99.0 g of benzene
has a boiling point of 80.31°C. Determine the molar mass of this compound. (Boiling point of
pure benzene = 80.10°C and Kb for benzene = 2.53°C kg mol–1).
29. (a) Complete the following chemical reaction equations:
(i) HgCl2(aq) + PH3(g) ¾
¾®
(ii) SiO2(s) + HF(g) ¾
¾®
(b) Explain the following observations:
(i) Sulphur in vapour state exhibits paramagnetic behaviour.
(ii) The stability of +3 state increases down the group in group 15 of the periodic table.
(iii) XeF2 has a linear shape and not a bent structure.
Examination Papers 155
OR
(a) Complete the following chemical reaction equations:
(i) AgCl(s) + NH3(aq) ¾
¾®
(ii) P4(s) + NaOH(aq) + H2O(l) ¾
¾®
(b) Explain the following observations:
(i) H2S is less acidic than H2Te
(ii) Fluorine is a stronger oxidising agent than chlorine
(iii) Noble gases are the least reactive elements.
30. (a) How will you prepare the following compounds starting with benzene?
(i) Benzaldehyde
(ii) Acetophenone.
(b) Give chemical tests to distinguish between the following pairs of compounds:
(i) Ethanal and Propanal
(ii) Benzaldehyde and Acetophenone
(iii) Phenol and Benzoic acid.
OR
(a) Explain the mechanism of nucleophilic attack on a carbonyl group of an aldehyde or a ketone.
(b) How would you bring about the following conversions?
(i) Propanone to Propene
(ii) Ethanol to 3-hydroxybutanal
(iii) Benzaldehyde to Benzophenone.
Solutions
CBSE (Foreign) SET–I
1. One atom.
2. Second order
3. ZSM–5
4. HI is stronger acid then HCl because dissociation energy of H–I bond is less than that of H–Cl.
5. An ambidentate ligand is one which can link through either of the two donor atoms to the central
metal ion. For example: NO–2 and O NO, CN and NC.
Br
|
6. CH3 — CH— CH — CH — CH3
5 4 |3 2 1
CH3
7. 4-Methyl-pent-3-en-2-one
8. When glucose is treated with bromine water it forms gluconic acid.
Br /H O
HOCH2 — (CHOH) 4 — CHO ¾ ¾2 ¾¾
2
® HOCH2 — (CHOH) 4 — COOH
Gluconic acid
Br F
F
Bent T–shaped
Xe
F F
O
Square pyramidal
13. (i) Preparation of potassium dichromate from sodium chromate
(a) 2Na 2 CrO4 + H2 SO4 ¾
¾® Na 2 Cr2 O7 + Na 2 SO4 + H2 O
(b) Na 2 CrO7 + 2KCl ¾
¾® K 2 Cr2 O7 + 2NaCl
(ii) Preparation of KMnO4 from K2MnO4
2K2MnO4 + Cl2 ¾
¾® 2KMnO4 + 2KCl
OR
2K2MnO4 + H2O + O3 ¾¾® 2KMnO4 + 2KOH + O2
14. (i) [Cr (H2O)2 (C2O4)2]–
(a) Hybridization — d 2 sp 3
(b) Shape — octahedral
(c) Magnetic behaviour — Paramagnetic
(ii) [Co (NH3)2 (en)2]3+
(a) Hybridisation — d 2 sp 3
(b) Shape — Octahedral
(c) Magnetic behaviour — diamagnetic
OR
(i) Crystal field splitting in an octahedral field.
According to C.F.T at first there is an increase in the energy of d-orbitals relative to that of the
free ion just as would be the case in spherical field. The two orbitals lying along the axis get
repelled more strongly than other three (dxy, dyz, dxz). The degenerate set of d-orbitals get split
into two sets: the lower energy t2g set and eg set. The energy separation is denoted by D o . The
actual configuration adopted is decided by the relative values of D o and P. P-represents the
energy required for electron pairing in a single orbital.
(a) If D o < P then fourth electron goes to e g
(b) When D o > P, then fourth electron pairs the t2g orbital.
Examination Papers 159
Energy
Barycentre
DO
Metal
d-orbitals Average energy
of d- orbitals in a t2g
spherical crystal dxy, dyz, dxz
field
dx2 – y2, dz2 dxy, dyz, dxz Splitting of orbitals
in an octahedral
Five degenerate
crystal field.
d-orbitals in free
metal ion
(ii) Spectrochemical Series: It is a series in which ligands can be arranged in the order of
increasing field strength or in order of increasing magnitude of splitting they produce.
The order is
I - < Br - < SCN- < Cl - < S 2 - < F - < OH- < C 2 O24 - < H2 O < NCS < edta 4- < NH3
< en < CN- < CO
15. (i) Mechanism of hydration of ethene to ethanol
Step-I: Protonation of alkene
H H
H H +
+
C C + H O H H C C H + H 2O
H H
H H
Step-II: Nucleophilic attack of water as carbocation
H H H H
+ +
H C C H + HO
2 H C C O H
H H H H
Step-III: Deprotonation of alcohol
H H H H OH
+
+
H C C O H + HO
2 H C C H + H3 O
H H H H
(ii) Mechanism of dehydration of ethanol to ethene.
Step-I: Formation of protonated alcohol
H H H H H
Fast +
H C C O H + H+ H C C O H
H H H H
Ethyloxonium ion
160 Xam idea Chemistry—XII
H H
H H
+ +
H N + H H N H
H H
(ii) The boiling points of primary amine are higher than the tertiary amines because strong
intermolecular hydrogen bonding takes place between the molecules of primary amine.
CH3
H 3C N d– H d+ N d– H d+
H d+ H d+
Examination Papers 161
(ii) C 6 H5 N2 Cl + H3 PO2 + H2 O ¾
¾® C 6 H6 + N2 + HCl + H3 PO3
Benzene diazonium Benzene
chloride
19. Given: Z = 2
a = 286.65 pm d = 7.874 g cm–3
M = 56 g mol–1 NA = ?
ZM
d=
(a 3 ) ´ N A
2 ´ 56
7.874 =
(286.65) ´ 10 -30 ´ N A
3
2 ´ 56 112 112 ´ 10 23
\ NA = = =
7.874 ´ ( 286.65) 3 ´ 10 -30 18.5 ´ 10 -23 18.5
NA = 6.054 × 1023
20. Electrochemical cell
Zn(s)| Zn2+ (.10 M) | | Ag+ (conc.) | Ag (s)
E ocell = E oR - E oL
= 0.80 (– 0.763)V = 1.563 V
We know that
0.0591 [Zn 2 + ]
E ocell = (E oR - E oL ) - log
n [Ag + ] 2
0.0591 [0.10]
1.48 = 1.563 – log
2 [Ag + ] 2
0.10 0.083
log = = 2.8087
+ 2 0.02955
[Ag ]
0.10
Or = antilog of 2.8087 = 643.7
[Ag + ] 2
010
.
[Ag+]2 = = 1.553 × 10 -4
643.7
\ [Ag+] = 1.247 × 10–2 M
21. (i) Macro molecular colloids: Macromolecules in suitable solvents form solution. Where in size
of the macromolecules may fall within the colloidal range. The system showing such
characteristics are called macromolecular colloids. The colloids are quite stable and in many
respect they resemble true solutions. Examples of naturally occurring macro molecules are
starch, cellulose, proteins and those of manmade macromolecules are nylon, polythene,
polystyrene, synthetic rubber etc.
162 Xam idea Chemistry—XII
(ii) Multimolecular colloids: A large number of atoms or smaller molecules (diameter < 1 nm) of
a substance on dissolution aggregate together to form species having size in the colloidal
range. Such species are called multimolecular colloids. Example: A sulphur sol contains
thousands of S8 sulphur molecules, a platinum or gold sol may have particles of various sizes
having many atoms.
(iii) Associated colloides (Micelles): There are certain substances which at low concentrations
behave like normal strong electrolytes but at higher concentration behave as colloidal solutions
due to the formation of aggregated particles. Such colloids are associated colloids and
aggregated particles as micelles. Examples: soaps and detergents.
22. (i) This is because transition metals have strong metallic bonds as they have large number of
unpaired electrons.
(ii) There is a close similarity in physical and chemical properties of the 4d and 5d series of the
transition elements much more than expected on the basis of usual family relationship. This is
because 5d and 4d series elements have virtually the same atomic and ionic radii due to
lanthanide contraction. Due to equality in size of Zr and Hf, Nb and Ta, Mo and W, etc., the
two elements of pair have the same properties.
(iii) The members in the actinoid series exhibit larger number of oxidation states than the
corresponding members in the lanthanide series due to the fact that the 5f, 6d and 7s levels are
of comparable energies.
H H
|
|
23. (i) CH3 —C*— CH2 CH3 CH3 — C — CH3
| |
OH OH
(Chiral) (Non -chiral)
(ii) CH3CHClCH2CH3, in more easily hydrolysed as it forms secondary carbocation which is more
stable than primary carbocation.
(iii) 1–bromopentane will react faster in SN2 displacement reaction as it is a 1° alkyl halide.
24. (i) Pig iron into steel: Pig iron is converted into steel by heating in a converter. A blast of oxygen
diluted with carbon dioxide is blown through the converter. Oxygen reacts with impurities and
raised the temperature to 2173K carbon gets oxidised to CO which burns off at the mouth of
the converter. Oxides of silicon and Mg form slag. When the flame is stopped, slag is tapped
off and other metals like Mn, Cr, Ni, W may be added in the end.
(ii) Bauxite into pure alumina.
(a) Al 2 O3 ( s) + 2NaOH( aq) + 3H2 O(l) ¾
¾® 2Na [Al (OH) 4 ]( aq)
Anode: Cu ¾¾® Cu 2 + + 2e
Cathode: Cu 2+ + 2e ¾
¾® Cu (Pure copper)
25. (i) Invert Sugar: The dextrorotatory sucrose when hydrolysed by boiling with mineral acid
produces an equal number of molecules of dextrorotatory fructose. The resulting mixture is
laevorotatory and termed as invert sugar.
H+
C12 H22 OH + H2O ¾¾¾
¾® C6H12O6 + C6H12O6
Sucrose Glucose Fructose
[a]D = 66.5° [a]D = 52.5° [a]D = – 93°
Invert sugar
O
||
(ii) Peptide linkage: The amide linkage (— C — NH —) formed between two a–amino acid
molecules with the loss of a water molecule in a polypeptide is called a peptide linkage.
(iii) Denaturation of Proteins: When a protein in its native form, it is subjected to a change,
change in temperature or change in pH, the hydrogen bond are disturbed. Due to this, globules
unfold and helix get uncoiled and protein loses its biological activity. This is called
denaturation of protein. During denaturation 2° and 3° structures are destroyed but 1°
structures remain intact, e.g., coagulation of egg white on boiling, curdling of milk, etc.
OR
The following reactions cannot be explained by the open chain structure of glucose.
(i) Despite having the aldehyde group, glucose does not give 2, 4– DNP test, Schiffs test and it
does not form the hydrogensulphite addition product with NaHSO3.
(ii) The penta acetate of glucose does not react with hydroxyl amine indicating the absence of free
—CHO group.
(iii) D–Glucose on treatment of methyl alcohol in the presence of dry HCl gas gives two isomeric
nonomethyl derivatives known as a-D-glucoside and methyl b– D–glucoside. These
glucosides do not reduce fehling solution and also do not react with hydrogen cyanide
indicating the absence of free —CHO group.
A ring structure called pyranose structure (a- or b-) is proposed for the glucose molecule.
26. Polymers are classified into four groups based on the magnitude of intermolecular forces. They are—
(i) Elastomers (ii) Fibers
(iii) Thermoplastic polymers (iv) Thermosetting polymers
Polythene—Polythene is a thermoplastic polymer.
Bakelite— It is a thermosetting polymer.
27. Antiseptics: Antiseptics are the chemicals which prevent the growth of the harmful microorganism.
They do not harm the living tissues. For example dettol.
Disinfectants: These are the chemicals which completely destroy the microorganism: They are toxic
to living tissues. 1% solution of phenol is a disinfectant whereas 0.2% solution of phenol is antiseptic.
28. (a) Positive deviation from Raoult's law: When the partial vapour pressure of each component
(A and B) consequently the total vapour pressure is greater than the pressure expected on the
basis of Raoult's law then the deviation is termed as positive deviation.
164 Xam idea Chemistry—XII
Cause of positive deviation: This type of deviation is observed by solution in which the
forces of attraction between A–A molecules and between B–B molecules is greater then the
forces of attraction between A–B molecules.
g A - B < g A -A or g B- B
Negative deviation from Raoult's law: When the partial vapour pressure of each component
of solution is less than the vapour pressure expected on the basis of Raoult's law then the
deviation is called as negative deviation.
Causes of negative deviation: This type of deviation is shown by solutions in which the
forces of attraction between A–A and B–B molecules is less than the forces of attraction
between A and B molecules.
g A - B > g A -A or g B- B
–1
(b) Given: MB = 58.5 g mol
WA = 65g, WB = ?
DTf = 7.5°C or 7.5 K,
Kf = 1.86 K kg mol–1
i = 1.87
We know that,
WB 1000
DTf = iKf × ´
M B WA
WB 1000
7.5 = 1.87 × 1.86 × ´
58 . 5 65
7. 5 ´ 58 . 5 ´ 65
\ WB =
1. 87 ´ 1. 86 ´ 1000
28518.75
WB =
3478.2
WB = 8.199 g.
OR
(a) Osmosis: The phenomenon in which solvent molecules flow through a semipermeable
membrane from a solution of low concentration to a solution of higher concentration is termed
as osmosis.
Osmotic Pressure: The hydrostatic pressure exerted by the column of the solution which is
just sufficient to prevent the osmosis is called osmotic pressure.
Advantage of using osmotic pressure as compared to other collegative properties:
(i) The equilibrium is established very quickly. Hence, results are obtained in a very short
time.
(ii) The concentration of the solution does not change during determination of osmotic
pressure.
(iii) This is ideal method for proteins to find their molar mass since it happens at room
temperature and no coagulation occurs.
Examination Papers 165
CH3 CHO
30. CH3Cl, Anhy. AlCl3 (i) CrO2Cl2, CS2
(a) (i)
(ii) H3O+
COCH3
CH3COCl
Anhy. AlCl3
(ii)
Benzene Acetophenone
I2, NaOH
CHI3 ¯ + + 3NaI + 3H 2O
3– +
6 + FeCl3 [Fe(C6H5O)6] + 3H + HCl
Violet-complex
OR
(a) Mechanism of nucleophilic addition reactions:
A nucleophile attacks the electrophilic carbon atom of the polar carbonyl group from a
direction approximately perpendicular to the plane of sp2 hybridized orbitals of carbonyl
carbon. The hybridization of carbon changes from sp2 to sp3 in this process and a tetrahedral
intermediate is produced. The intermediate captures a proton from the medium to give the
neutral product.
Nu Nu
l lfast
d+ d– slow – H
+
C O + Nu C O C O H
step-1
Aldehyde or ketone Tetrahedral step-2 Addition product
(Planar) intermediate
O OH
|| |
(i) CH3 — C— CH3 ¾LiAlH 4 conc. H 2 SO4
(b) ¾ ¾¾ ® CH3 — CH — CH3 ¾ ¾ ¾ ¾ ¾
¾® CH3 — CH = CH2
Propanone D Propene
OH
|
(ii) C 2 H5 OH ¾PCC dil NaOH
¾¾® CH3 CHO ¾ ¾ ¾ ¾® CH3 — CH— CH2 — CHO
Ethanol 3-hydroxy butanal
O O
12
O
7.8
pm
116.8°
O O O O O
O
H
+ d -d -d d+ Dry ether
(ii) C = O + CH3 C H2 — Mg Cl ¾¾¾® [ CH3 CH2 CH2 OMgCl]
Ethylmag. chloride Addition product
H
Methanal
H+, H O
¾ ¾ ¾ 2¾® CH3 CH2 CH2 OH + Mg(OH)Cl
Hydrolysis Propan -1-ol
-3 -8
3
d ´ a ´ NA 10. 5 g cm ´ (4 . 077 ´ 10 cm) ´ (6. 02 ´ 10 23 mol -1 )
3
19. M = =
Z 4
-3 -24
10.5 g cm ´ 67.767 ´ 10 cm ´ 6.02 ´ 10 23 mol -1
3
=
4
–1
= 107.09 g mol
20. Given Eo Ag+/Ag = 0.80V, Eo Cu 2 + /Cu = + 0.34V
[Cu2+] = 0.10 M [Ag+] = ?
Eocell = EoR – EoL = 0.80 – 0.34V = 0.46V
From Nernst Equation:
168 Xam idea Chemistry—XII
0.0591 [ Cu 2 + ]
Ecell = Eocell - log
2 [Ag + ] 2
0.591 [ 010
. ]
0.422 = 0.46 - log
2 [Ag + ] 2
010
.
log = 1.2881
[Ag + ] 2
[Ag+]2 = 0.0051
\ [Ag+] = 7.1× 10–2 M
21. (i) The positively charged colloidal particles of Fe(OH) 3 get coagulated by the oppositely
charged Cl– ions provided by NaCl.
(ii) On passing direct current, colloidal particles move towards the oppositely charged electrode
where they lose their charge and get coagulated.
(iii) Scattering of light by the colloidal particles takes place and the path of light becomes visible
(Tyndall effect).
26. Biodegradable detergents: Detergents having straight hydrocarbon chains are easily degraded by
micro-organism and hence called biodegradable detergents, e.g., sodium–4–(1-dodecyl) benzene
sulphonate.
+
CH3 ¾ (CH2 ) 11 ¾ ¾ SO-3 Na
Non-biodegradable detergents: Detergents having branched hydrocarbon chains are not easily
degraded by micro-organisms and hence are called non-biodegradable detergents, e.g.,
sodium-4-(1, 3, 5, 7-tetramethyl octyl) benzenesulphonate.
CH3 CH3
½ ½ +
CH3 ¾ ( CH ¾ CH2 ¾ ) 3 ¾ CH ¾ ¾ SO-3 Na
Non-biodegradable detergents accumulate in rivers and waterways thereby causing water pollution.
27. (i) CH2 = CHCl Vinyl chloride
(ii) CF2 = CF2 Tetrafluoroethene
(iii) Phenol and formaldehyde
F
H
O
12. (i) Xe (ii) Cl
O O O
HClO4 (Perchloric acid)
F
XeF2 (Linear shape)
General Instructions:
(i) All questions are compulsory.
(ii) Question numbers 1 to 8 are very short answer questions and carry 1 mark each.
(iii) Question numbers 9 to 18 are short answer questions and carry 2 marks each.
(iv) Question numbers 19 to 27 are also short answer questions and carry 3 marks each.
(v) Question numbers 28 to 30 are long answer questions and carry 5 marks each.
(vi) Use log tables, if necessary. Use of calculators is not allowed.
(a) Calculate the rate constant. Include units with your answer.
(b) What will be the concentration of N2O5 after 100 minutes?
(c) Calculate the initial rate of reaction.
21. Explain how the phenomenon of adsorption finds application in each of the following processes:
(i) Production of vacuum
(ii) Heterogeneous catalysis
(iii) Froth floatation process
OR
Define each of the following terms:
(i) Micelles
(ii) Peptization
(iii) Desorption
Examination Papers 173
COOH
(ii) ¾SoCl
¾¾2 ®
heat
COOH
H3 O+
(iii) C6H5CONH2 ¾ ¾ ¾¾®
heat
30. (a) Explain the following:
(i) NF3 is an exothermic compound whereas NCl3 is not.
(ii) F2 is most reactive of all the four common halogens.
(b) Complete the following chemical equations:
(i) C + H2 SO4 (conc.) ¾ ¾®
(ii) P4 + NaOH + H2O ¾¾®
(iii) Cl 2 + F2 ¾
¾®
(excess)
OR
(a) Account for the following:
(i) The acidic strength decreases in the order HCl > H2S > PH3.
(ii) Tendency to form pentahalides decreases down the group in group 15 of the periodic
table.
(b) Complete the following chemical equations:
(i) P4 + SO2 Cl 2 ¾¾®
(ii) XeF2 + H2 O ¾
¾®
(iii) I 2 + HNO3 ¾
¾®
(conc)
Examination Papers 175
Solutions
CBSE (Delhi) SET - I
1. Crystalline solids are anisotropic in nature means some of their physical properties like electrical
conductivity, refractive index, etc., are different in different directions.
k ´ 1000
2. l m = , where k is the conductivity and C is the molar concentration.
C
3. The movement of colloidal particles under an applied electric potential is called electrophoresis.
8+2 F
4. Total no. of electron pairs in the valence shell of central Xe atom = =5
2
No. of bond pairs = 2
No. of lone pairs = 3
Therefore, the shape of molecule would be linear. Xe
CH3
5.
|
CH3 — C— CH2 — Br 1- Bromo - 2, 2- dimethyl propane
| F
CH3
CH3 O
6. | ||
CH3 — C H — CH2 — C — H
7. Increasing order of solubility of amines in water
C6H5NH2 < (C2H5)2NH < C2H5NH2
8. Polymers which get disintegrated by themselves in biological systems during a certain period of time
by enzymatic hydrolysis or to some extent by oxidation are called biodegradable polymers. An
example of biodegradable polymer is PHBV, i.e., poly-b-hydroxy butyrate-co-b hydroxyvalerate.
9. According to electrochemical theory of rusting the impure iron surface behaves like small
electrochemical cell in the presence of water containing dissolved oxygen or carbon dioxide. In this
cell pure iron acts as anode and impure iron surface acts as cathode. Moisture having dissolved CO2 or
O2 acts as an electrolyte. The reactions are given below.
At anode: Fe ¾ ¾® Fe 2+ + 2e – ; E o 2+ = - 0.44 V
Fe / Fe
1
At cathode: 2H + O2 + 2e – ¾
+
¾® H2 O; E ° H + / O / H O = 1.23V
2 2 2
1
Overall reaction: Fe + 2H+ + O2 ¾ ¾® Fe 2+ + H2 O; E ° cell = 1.67V
2
The Fe2+ ions are further oxidised by atmospheric oxygen to Fe3+ ions, which comes out in the form of
hydrated ferric oxide (rust).
1
2Fe 2+ + O2 + 2H2 O ¾ ¾® Fe 2 O3 + 4H+
2
Fe2O3 + xH2O ¾ ¾® Fe2O3 xH2O (Rust)
178 Xam idea Chemistry—XII
OH ONa OH
é ONa ù
½ ê ú ½ ½
CHCl 3 + NaOH ê ½ ú NaOH — CHO H O+ — CHO
3
¾¾¾¾¾¾® ê — CHCl 2 ú ¾¾® ¾®
340K ê ú
ê ú Salicyaldehyde
Phenol
êë úû
(ii) Friedel–Crafts acylation of anisole: Anisole on treatment with acylchloride in the presence
of anhydrous AlCl3 undergo electrophilic substitution in the ring at ortho and para positions.
For example,
OCH3 OCH3 OCH3
O
–
–
O
–
–
–
–
O
p-Methoxy acetophenone
(major product)
OH OH OH
½ ½ ½
H 2 SO4 (conc.) — SO3 H HNO3 (conc.) O2 N — — NO2
15. (i)
¾¾¾¾¾® ¾¾¾¾®
| |
Phenol
SO3 H NO2
Phenol -2,4 Picric acid
disulphonic acid
16. | |
H — 1 C — OH HO — 1 C — H
| |
2 2
H — C — OH H — C — OH
| |
HO — 3 C — H HO — 3 C — H
O O
| |
4 4
H — C — OH H — C — OH
| |
5
H —5 C — H— C —
| |
6
CH2 OH CH2 — OH
a - D- (+)- Glucose b- D-(+ )- Glucose
180 Xam idea Chemistry—XII
In a-D Glucose, the —OH group at C1 is toward right whereas in b-glucose, the -OH group at C1 is
towards left. Such a pair of stereo-isomers which differ in the configuration only around C1 are called
anomers.
17. Primary Structure: The specific sequence in which the various a-amino acids present in a protein
are linked to one another is called its primary structure. Any change in the primary structure creates a
different protein.
Secondary Structure: The conformation which the polypeptide chain assumes as a result of
hydrogen bonding is known as secondary structure. The two types of secondary structures are a-helix
and b-pleated sheet structure.
In a-helix structure, the polypeptide chain forms all the possible hydrogen bonds by twisting into a
right handed screw (helix) with the —NH groups of each amino acid residue hydrogen bonded to the
C==O groups of an adjacent turn of the helix. In b-pleated structure, all peptide chains are stretched
out nearly to maximum extension and then laid side by side which are held together by hydrogen
bonds.
18. (i) Bakelite is used for making combs, electrical switches, handles of various utensils and
phonograph records.
(ii) Nylon-6 is used for making tyre cords, ropes and fabrics.
19. a = 400 pm
a
For fcc, r =
2 2
400 400 2 400 2
\ r= = ´ = = 100 2
2 2 2 2 2 4
Þ r = 100 × 1.414 = 141.4 pm
20. (a) When t = 20 min, [A] = 0.289 mol L–1
Also, [A]0 = 0.400 mol L–1
For a first order reaction
2.303 [A] °
k= log
t [A]
2.303 0.400
\ k= log
20 0.289
2.303 4.00
Þ k= log
20 2.89
2.303
Þ k= [log 4.00 – log 2.89]
20
2.303
Þ k= [0.6021 – 0.4609]
20
2.303
Þ k= ´ 01412
.
20
Þ k = 2.303 × 0.00706 = 0.016259 min–1
Þ k = 1.6259 × 10–2 min–1
Examination Papers 181
2.303 [A ]0
(b) t = log
k [A ]
Here, [A]0= 0.400 mol–1, t = 100 min, k = 1.626 × 10–2 min–1
2.303 0.400
\ 100 = -2
log
1.626 ´ 10 [A ]
100 ´ 1.626 ´ 10 -2 0.4
= log
2.303 [A ]
0.4
0.7060 = log
[A ]
0.4
Antilog (0.7060) =
[A ]
0.4
5.082 =
[A ]
0.4
Þ [A] = = 0.0787 M
5.082
(c) Initial rate, i.e., rate of reaction when t = 0
When, t = 0.00 min, [A] = 0.400 mol L–1
Also, k = 1.626 × 10–2 min–1
\ Initial rate = k [A] = 1.626 × 10–2 min–1 × 0.400 mol L–1
= 6.504 × 10–3 mol L–1 min–1.
21. (i) Production of Vacuum: Adsorption can be successfully applied to create conditions of high
vacuum. For this a bulb of charcoal cooled in liquid air, is connected to vessel which has
already been exhausted as far as possible by vacuum pump. The remaining traces of air inspite
of low pressure are adsorbed by the charcoal almost completely.
(ii) Heterogeneous Catalysis: There are many gaseous reactions of industrial importance
involving solid catalyst. Manufacture of ammonia using iron as a catalyst, manufacture of
H2SO4 by contact process using V2O5 catalyst and use of finely divided nickel in the
hydrogenation of vegetable oils are the excellent examples. The gaseous reactants are adsorbed
on the surface of the solid catalyst. As a result, the concentration of the reactants increases on
the surface of the catalyst and hence the rate of reaction increases.
(iii) Froth Floatation Process: In froth floatation process the powdered ore is mixed with water. It
is then mixed with pine oil (a frother). The oil particles are adsorbed on the surface of ore
particles. Now, a stream of air is blown through the mixture from below when froth is formed
at the water surface. The ore particles stick to the bubbles of the air rises to surface along with
the foam while the gangue particles which are wetted by water settle at the bottom. The foam is
separated out and is collected and in the course, the ore particles also settle down.
OR
(i) Micelles: There are some substances which at low concentration behave as normal strong
electrolytes but at higher concentration exhibit colloidal behaviour due to formation of
aggregated particles. The aggregated particles thus formed are called micelles. The formation
182 Xam idea Chemistry—XII
of micelles takes place only above a particular temperature called Kraft temperature and
above a particular concentration called critical micelle concentration (CMC). Surface active
agents such as soap and synthetic detergents belong to this class.
(ii) Peptization: The process of converting a precipitate into colloidal sol by shaking it with
dispersion medium in the presence of a small amount of suitable electrolyte is called
peptization. During peptization, the precipitate absorbs one of the ions of the electrolyte on its
surface. This causes development of positive or negative charge on precipitates, which
ultimately break up into particles of colloidal dimension.
(iii) Desorption: The process of removing an adsorbed substance from a surface on which it is
adsorbed is called desorption.
22. (i) Vapour phase refining of a metal: In this method, the metal is converted into its volatile
compound and collected elsewhere. It is then decomposed to give pure metal. For example,
refining of nickel by Mond process.
Ni + 4CO ¾330 ¾-¾ 350 K
¾® Ni(CO)4
450 – 470 K
Ni(CO)4 ¾¾¾¾ ¾® Ni + 4CO
(ii) Electrolytic refining of a metal: In this method, the impure metal is made to act as anode. A
strip of same metal in pure form is used as cathode. They are put in a suitable electrolytic bath
containing soluble salt of same metal. When electric current is passed the metal from the anode
goes into solution as ions due to oxidation while pure metal gets deposited at the cathode due to
reduction of metal ions. The voltage applied for electrolysis is such that impurities of more
electropositive metals remains in the solution as ions while impurities of the less electropositive
metals settle down under the anode as anode mud.
–
At anode: ¾® M n + + n e
M ¾
–
At cathode: Mn+ + n e ¾
¾® M
(iii) Recovery of silver after silver ore was leached with NaCN: During leaching Ag is
oxidised to Ag+ which then combines with CN– ions to form soluble complex, [Ag(CN)2]–.
Silver is then recovered from this complex by displacement method using more
electropositive zinc metal.
2[Ag(CN)2]–(aq) + Zn(s) ¾
¾® 2Ag(s) + [Zn(CN)4]2–(aq)
23. (i) MnO4– + 8H+ + 5e ¾® Mn2+ + 4H2O] × 2
¾
C2O42– ¾® 2CO2 + 2e ] × 5
¾
24.
Name of the Complex Hybridisation of metal Geometry of complex Magnetic behaviour
ion involved
Potassium hexacyano d2sp3 Octahedral Paramagnetic
manganate (II)
Pentaammine Chloridocobalt d2sp3 Octahedral Diamagnetic
(III) Chloride
Potassium tetra dsp2 Square planar Diamagnetic
cyanonikelate (II)
25. (i) Haloalkanes dissolve in organic solvents because the new intermolecular attractions between
haloalkanes and organic solvent molecules have much the same strength as ones being broken
in the separate haloalkanes and solvent molecules.
(ii) An equimolar mixture of a pair of enantiomers is called racemic mixture. For example,
butan-2-ol. A racemic mixture is optically inactive due to external compensation.
(iii) Of the two bromo derivatives, C6H5CH(CH3)Br and C6H5CH(C6H5)Br, the intermediate
obtained from C6H5CH (C6H5) Br is more stable than obtained from C6H5CH(CH3) Br because
it is stabilised by two phenyl groups due to resonance. Therefore, C6H5CH (C6H5)Br is more
reactive than C6H5(CH3) Br.
26. H H
+ +
(a) R — N + H R—N —H
H H
Due to electron releasing nature, the alkyl group (R) pushes electrons towards nitrogen in alkyl
amine and thus makes the unshared electron pair more available for sharing with the proton of
the acid. Therefore alkyl amine are more basic than ammonia.
+ – + –
NH2 N2Cl N2BF4 NO2
+ –
NH2 N2Cl I
NaNO2/HCl +KI
(ii)
273-278 K
27. (i) Detergents: Detergents are cleansing agents which have all the properties of soaps, but actually
do not contain any soap e.g., sodium dodecylbenzene sulphonate. These can be used both in
soft and hard water as they give foam even in hard water. Detergents are mainly classified into
three categories:
184 Xam idea Chemistry—XII
CH3COCH3 ¾Tollen's
¾ ¾® No silver mirror
reagent
OH
dil. NaOH D
(b) (i) CH3CHO CH3CH—CH2CHO CH3CH—CHCHO
Ethanal But-2-enal
–+
CH2CH3 COOK COOH
KMnO4–KOH H3O+
(iii)
D
OR
(a) (i) Cannizzaro reaction: Aldehydes which do not have an a-hydrogen atom undergoes
disproportionation reactions on treatment with concentrated alkali to give a mixture of
carboxylic acid salt and alcohol.
+
2 HCHO ¾Conc.
¾ ¾NaOH
¾
¾® HCOO Na + CH3 - OH
Formaldehyde Sod.formate Methyl alcohol
(ii) Decarboxylation: Carboxylic acids lose carbon dioxide to form hydrocarbons when their
sodium salts are heated with sodalime.
– +
RCOO Na ¾NaOH
¾ ¾and¾CaO
¾® RH + Na 2 CO3
D
186 Xam idea Chemistry—XII
–+
CH2CH3 COOK
(b) (i) KMnO4
KOH, heat
Ethyl benzene Pot. benzoate
COOH COCl
(ii) SOCl2
30. (a) (i) This is because bond dissociation energy of F2 is lower than Cl2 Moreover, fluorine forms
stronger bond with nitrogen due to comparable size.
(ii) Because of low F—F bond dissociation enthalpy.
(b) (i) C + 2H2SO4 (conc.) ¾¾® CO2 + 2SO2 + 2H2O
(ii) P4 + 3NaOH + 3H2O ¾ ¾® PH3 + 3NaH2PO2
Phosphine
573 K
(iii) Cl 2 + 3F2 ¾ ¾¾® 2ClF3
(excess)
OR
(a) (i) As bond dissociation enthalpy of H—Cl bond is lower than H—S which is lower than
P—H. The acidic strength decreases because of decrease in polarity of E—H bond from
H—Cl to P—H which is due to decrease in electonegativity of E.
(ii) This is due to inert pair effect. The stability of +5 oxidation state decreases down the
group in group 15.
(b) (i) P4 + 10SO2Cl2 ¾¾® 4PCl5 + 10SO2
(ii) 2Xe F2 + 2H2O ¾ ¾® 2Xe + 4HF + O2
(iii) 2HNO3 (conc.) ¾ ¾® H2O + 2NO2 + (O)] × 5
I2 + 5(O) ¾¾® I2O5
I2 O5 + H2 O ¾¾® 2HIO3
I2 + 10HNO3(conc.) ¾
¾® 2HIO3 + 10NO2 + 4H2O
(ii) Zinc in the extraction of silver: Silver present in the ore is leached with dilute solution of
NaCN in the presence of air or oxygen to form a soluble complex.
4Ag(s) + 8CN–(aq) + 2H2O(l) + O2(g) ¾ ¾® 4 [Ag (CN)2]– + 4 OH–(aq)
Soluble Complex
Silver is then recovered from the complex by displacement method using complex using a more
electropositive zinc metal.
2[Ag(CN)2]– (aq) + Zn(s) ¾ ¾® 2Ag(s) + [Zn(CN)4]2–(aq)
(iii) Silica in the extraction of copper: During smelting and bessemerisation the impurity ferrous
sulphide oxidised to ferrous oxide which is then reacted with silica (flux) to form slag ferrous silicate.
FeO + SiO2 ¾ ¾® FeSiO3
Flux Ferrous silicate(slag)
(ii) Enzymes: Enzymes are catalysts of biological origin which accelerate various cellular reactions
without themselves undergoing any apparent change during the course of action. Enzymes are
highly specific in their action on substrate. Almost all the enzymes are globular proteins.
(iii) Analgesics: Analgesics are chemical compounds which are used for relieving pain. Analgesics
relieves pain by acting on central nervous system or on peripheral pain mechanism, without
significantly affecting consciousness. There are two types of analgesics:
Narcotics — Morphine, cocaine, heroine
Non-narcotics — Aspirin, ibuprofen etc.
28. (a) (i) Henry’s law: It states that the partial pressure of the gas in vapour phase (p) is
proportional to the mole fraction of the gas (x) in the solution and is expressed as:
P = KH x
Where KH is Henry’s law constant
(ii) Raoult’s law: It states that for any solution the partial pressure of each volatile
component in the solution is directly proportional to its mole fraction.
W ´ R ´T
(b) MB = B
p´ V
Here, WB = 8.95 mg = 8.95 × 10–3g, R = 0.0821 L atm K–1 mol–1
0.335
T = (25 + 273 ) K = 298 K , p = atm
760
V = 35 × 10–3 L
Substituting these values in the above equation
8.95 ´ 10 -3 g ´ 0.0821 L atm K -1 mol –1 ´ 298 K
We get, MB =
0.335
atm ´ 35 ´ 10 -3 L
760
MB = 14193. 29 g mol–1
OR
(a) Molarity (M): It is defined as number of moles of solute dissolved in one litre of solution.
Moles of solute
Molarity =
Volume of solution in litre
Unit of molarity is mol L–1 or M (molar). Molarity changes with change in temperature as
volume changes with change in temperature.
Molality (m): It is defined as the number of moles of the solute dissolved in one kilogram (kg)
of the solvent and is expressed as:
Moles of solute
Molality =
Mass of solvent (in kg)
Number of moles of solute
= ´ 1000
Mass of solvent (in grams)
Unit of molality is mol kg–1.
Molality is independent of temperature.
K ´ WB ´ 1000
(b) MB = b
DTb ´ WA
Here, Kb = 3.63K kg mol–1, WB = 6.21 g
Examination Papers 189
Z´M Z´M
19. d =
3
Þ a3 = ...(i)
a ´ NA d ´ NA
For fcc unit cell, Z = 4
M = 207 g mol–1 NA = 6.02 × 1023 mol –1
d = 11.35 g cm–3
Substituting these values in equation (i), we get
4 ´ 207 g mol -1
a3 =
11.35g cm -3 ´ 6.02 ´ 10 23 mol -1
1/ 3
4 ´ 207 ´ 10 æ 8280 ö
a3 = 24
cm 3 Þ a = çç ÷÷ ´ 10 -8 cm
11.35 ´ 6.02 ´ 10 è 11.35 ´ 6.02 ø
1/ 3
æ 8280 ö
Let x = çç ÷÷
è 11.35 ´ 6.02 ø
1 1
log x = [ log 8280 – log11.35 – log 6.02] = [3.9180 - 1.0549 - 0.7796]
3 3
1
log x = [2.0835] = 0.6945
3
x = Antilog (0.6945) Þ x = 4.949
\ a = 4.949 × 10–8 cm Þ a = 494.9 pm
a
For fcc, r=
2 2
494.9 494.9 2 494.9 ´ 1.414
\ r= pm = pm = pm
2 2 4 4
\ r = 174.95 pm
26. (i) CH3CH2Cl ¾NaCN
¾¾® CH3CH2CN ¾Reduction ¾ ¾¾® CH3CH2CH2NH2
Ni / H 2
27. (i) Hard water contains calcium and magnesium salts. In hard water, soaps get precipitated as
calcium and magnesium soaps which being insoluble stick to the clothes as gummy mass.
(ii) Chloroxylenol and a-terpineol in a suitable solvent.
(iii) Antiseptics are chemical substances which prevent the growth of microorganisms and may
even kill them but are not harmful to human or animal tissues. Examples are dettol and savlon.
They are generally applied on wounds, ulcers, cuts and diseased skin surfaces. Furacin and
soframycin are well-known antiseptic creams.
Disinfectants are chemical substances which kill microorganisms but are not safe to be applied
to the living tissues. These are generally used to kill microorganisms present in the toilets, drains,
floors, etc. Some common examples of disinfectants are phenol (³1% solution) and chlorine (0.2
to 0.4 ppm).
CBSE EXAMINATION PAPERS
ALL INDIA–2011
Time allowed : 3 hours] [Maximum marks : 70
General Instructions:
(i) All questions are compulsory.
(ii) Question numbers 1 to 8 are very short answer questions and carry 1 mark each.
(iii) Question numbers 9 to 18 are short answer questions and carry 2 marks each.
(iv) Question numbers 19 to 27 are also short answer questions and carry 3 marks each.
(v) Question numbers 28 to 30 are long answer questions and carry 5 marks each.
(vi) Use log tables, if necessary. Use of calculators is not allowed.
23. Rearrange the compounds of each of the following sets in order of reactivity towards SN2
displacement:
(i) 2-Bromo-2-methylbutane, 1-Bromopentane, 2-Bromopentane
(ii) 1-Bromo-3-methylbutane, 2-Bromo-2methylbutane,
3-Bromo-2-methylbutane
(iii) 1-Bromobutane, 1-Bromo-2, 2-dimethylpropane,
1-Bromo-2-methylbutane
24. How would you obtain the following:
(i) Benzoquinone from phenol
(ii) 2-Methylpropan-2-ol from methylmagnesium bromide
(iii) Propan-2-ol from propane
25. State reasons for the following:
(i) pKb value for aniline is more than that for methylamine.
(ii) Ethylamine is soluble in water whereas aniline is not soluble in water.
(iii) Primary amines have higher boiling points than tertiary amines.
26. Draw the structures of the monomers of the following polymers:
(i) Polythene
(ii) PVC
(iii) Teflon
27. What are the following substances? Give one example of each.
(i) Food preservatives
(ii) Synthetic detergents
(iii) Antacids
28. (a) What type of a battery is lead storage battery? Write the anode and cathode reactions and the
overall cell reaction occurring in the operation of a lead storage battery.
(b) Calculate the potential for half-cell containing
0.10M K2Cr2O7 (aq), 0.20Mcr3+ (aq) and 1.0×10–4MH+(aq) The half cell reaction is
Cr2O72–(aq) + 14H+(aq) + 6e– ¾ ¾® 2Cr3+(aq) + 7H2O(l)
and the standard electrode potential is given as E° =1.33V.
OR
(a) How many moles of mercury will be produced by electrolysing 1.0 M. Hg(NO3)2 solution with
a current of 2.00 A for 3 hours?
(b) A voltaic cell is set up at 25° C with the following half-cells Al3+ (0.001 M) and Ni2+ (0.50 M).
Write an equation for the reaction that occurs when the cell generates an electric current and
determine the cell potential.
o o
(Given: E Ni 2+ = –0.25 V, EAl
/ Ni 3+
/Al
= –1.66 V)
COOH
(ii) C6H5CHO ¾H¾
2 NCONHNH 2
¾¾¾ ¾®
(iii) CH2 ¾ ¾
¾® CHO
H
H Br
H
6. Draw the structure of 2, 6-Dimethylphenol.
9. Define the following terms in relation to crystalline solids:
(i) Unit cell
(ii) Coordination number
Give one example in each case.
12. A reaction is of second order with respect to a reactant. How is the rate of reaction affected if the
concentration of the reactant is reduced to half? What is the unit of rate constant for such a reaction?
14. Describe the principle controlling each of the following processes:
(i) Zone refining of metals.
(ii) Electrolytic refining of metals.
15. Explain giving a suitable reason for each of the following:
(i) Transition metals and their compounds are generally found to be good catalysts.
(ii) Metal-metal bonding is more frequent for the 4d and the 5d series of transition metals than that
for the 3d series.
19. What mass of NaCl must be dissolved in 65.0 g of water to lower the freezing point of water by
7.50°C? The freezing point depression constant (Kf) for water is 1.86 C/m. Assume van’t Hoff factor
for NaCl is 1.87. (Molar mass of NaCl = 58.5 g).
22. Write the structures and names of all the stereoisomers of the following compounds:
(i) [Co(en)3]Cl3
(ii) [Pt(NH3)2Cl2]
(iii) [Fe(NH 3)4Cl2]Cl
Solutions
CBSE (All India) SET–I
1. Order of a reaction may be defined as the sum of the powers of the concentration terms of the
reactants in the rate law expression.
2. The catalysis in which the pore structure of the catalyst and the size of the reactant and product
molecules are comparable is called shape selective catalysis.
3. The naturally occurring chemical substances present in the earth’s crust which can be obtained by
mining are called minerals, while mineral from which metals can be extracted economically are called
ores.
4. The steady decrease in the atomic and ionic radii (having the same charge) with increase in atomic
number as we move across the series from lanthanum to lutetium is known as lanthanoid contraction.
5. 3-Bromoprop-l-ene
Cl O
| ||
6. CH3 — CH— CH2 — C — CH3
7. CH3CH2OH ¾conc.
¾¾ H 2 SO4
¾¾® CH2 = CH2 + H2O
443K
Ethanol Ethene
9. We can determine the atomic mass of an unknown metal by using the formula of density of its unit
cell.
Z (No. of atoms per unit cell) ´ M (atomic mass)
d (density) =
a 3 (cell edge) ´ NA (Avogadro number)
By knowing d, Z, a and NA, we can calculate M, the atomic mass of metal.
Z ´ volume of one atom
10. Packing efficiency = ´ 100
Volume of cubic unit cell
4
Z ´ pr 3
= 3 ´ 100
a3
For a simple cubic lattice, a = 2r and Z = 1
4
1´ pr 3
p
\ Packing efficiency = 3 3 ´ 100 = ´ 100
( 2r ) 6
= 52.36% = 52.4%
11. (i) Raoult’s law: It states that for any solution, the partial pressure of each volatile component in
the solution is directly proportional to its mole fraction.
(ii) Henry’s law: It states that the partial pressure of a gas in vapour phase (P) is proportional to its
mole fraction (x) in the solution.
12. An experimentally determined expression which relates the rate of reaction with the concentration of
reactants is called rate law while the rate of reaction when concentration of each reactant is unity in a
rate law expression is called rate constant.
(i) Comparing power of mole in L–1 mol s–1 and (mol L–1)1–n s–1,
We get
1=l–n Þ n = 0 i.e., zero order reaction
(ii) Again comparing power of mole in L mol s and (mol L–1) 1–n s–1, we get
–1 –1
2.303
t= log4
2.4 ´ 10 -3 s -1
2.303
= ´ 0.6021 s
2.4 ´ 10 -3
t = 577.7 s = 578 s
198 Xam idea Chemistry—XII
14. (i) In this method, the metal is converted into its volatile compound and collected elsewhere. It is
then decomposed to give pure metal.
Ti + 2 I 2 ¾500
¾¾ K
® Ti I 4
Impure
metal
Ti I 4 ¾1700
¾¾ K
® Ti + 2I 2
Pure metal
(ii) This method of concentration of ore is based upon the principle that the surface of sulphide
ores is preferentially wetted by oils while that a gangue is preferentially wetted by water.
15. (i) Cr2+ is reducing as its configuration changes from d4 to d3, a more stable half filled t2g
configuration while Mn3+ is oxidising as Mn3+ to Mn2+results a more stable half filled d5
configuration.
(ii) It is due to greater number of unpaired electrons in (n–1)d and ns orbitals at the middle of the
series.
16. (i) 8MnO4–(aq) + 3S2O32–(aq) + H2O (l) ¾
¾® 8MnO2(s) + 6SO42–(aq) + 2OH–(aq)
OR
(i) This is because Cu(I) ion is unstable in aqueous solution and undergo disproportionation.
2Cu + ( aq) ¾
¾® Cu 2+ ( aq) + Cu( s)
(ii) This is because due to lanthanoid contraction the expected increase in size does not occur.
O
||
17. (i) Peptide linkage: The amide (— C— NH—) linkage between two a-amino acids formed with
the loss of a water molecule is called a peptide linkage.
(ii) The six membered cyclic structure of glucose is called pyranose structure ( a - or b -), in
analogy with heterocylic compound pyran.
CH2OH
H O H
H
OH H
HO OH
H OH
a – D – (+) – Glucopyranose
2. DNA has double stranded a-helix structure. 2. RNA has single a-helix structure.
The common bases present in both DNA and RNA are adenine (A), guanine (G) and cytosine (C).
Examination Papers 199
WB ´ R ´ T
19. MB = ....(i)
p´ V
Here, WB = 8.95 mg = 8.95 × 10–3g , R = 0.0821 L atm mol–1 K–1
0. 335
T = 25°C = (25 + 273) K = 298 K , p = 0.335 torr = atm
760
V = 35 mL = 35 × 10–3 L
Substituting these values in the equation (i), we get
8.95 ´ 10 -3 g ´ 0.0821 L atm mol -1 K -1 ´ 298K ´ 760
MB = = 14193. 3 g mol–1
0.335 atm ´ 35 ´ 10 -3 L
20. These are of two types
(i) Hydrophilic
Stability: More stable as the stability is due to charge and water envelope surrounding the sol
particles.
Nature: Reversible
Examples: Starch, gum, etc.
(ii) Hydrophobic
Stability: Less stable as the stability is due to charge only.
Nature: Irreversible
Examples: Metal hydroxide like Fe(OH)3 and metal sulphide like As2S3.
OR
(i) On passing electric current through a sol, colloidal particles start moving towards oppositely
charged electrode where they lose their charge and get coagulated (electrophoresis).
(ii) Scattering of light by the colloidal particles takes place and the path of light becomes visible
(Tyndall effect).
(iii) The positively charged colloidal particles of ferric hydroxide sol get coagulated by the
oppositely charged Cl– ions provided by NaCl.
21. (i) This is because bond dissociation enthalpy of H—S bond is lower than that of H—O bond.
(ii) This is because two bonds share a double bond in the resonance hybrid structure of NO–2 while
three bonds share a double bond in the resonance hybrid structure of NO–3 . This is because
NO–2 has bond order 1.5 while NO–3 has bond order 1.33.
(iii) This is due to tendency of oxygen to form multiple bonds with metal atom.
22. (i) Ambidentate ligand: A ligand which can coordinate to central metal atom through two different
atoms is called ambidentate ligand. For example NO–2 ion can coordinate either through
nitrogen or through oxygen to a central metal atom/ion.
(ii) Denticity: The number of coordinating groups present in ligand is called the denticity of ligand.
For example, bidentate ligand ethane-1, 2-diamine has two donor nitrogen atoms which can
link to central metal atom.
·· ··
H2 N— CH2 — CH2 — N H2
Ethane–1, 2–diamine
200 Xam idea Chemistry—XII
(iii) The spliting of the degenerated d-orbitals into three orbitals of lower energy, t2g set and two
orbitals of higher energy eg, set due to the presence of ligand in a octahedral crystal field is
known as crystal spliting in a octahedral field.
23. (i) 1-Bromopentane > 2-Bromopentane > 2-Bromo-2methyl butane.
(ii) 1-Bromo-2-methyl butane > 3-Bromo-2-methyl butane > 2-Bromo-2-methyl butane
(iii) 1-Bromobutane > 1-Bromo-2-methylbutane > 1-Bromo-2,2-dimethyl butane.
OH O
Na2Cr2O7/H2SO4
24. (i)
Phenol
O
Benzoquinone
O é OMgBr ù OH
|| ê | ú |
(ii) CH3 — C— CH3 + CH3 MgBr ¾¾® êCH3 — C— CH3 ú ¾H¾
2O
¾ ® CH3 — C— CH3
ê | ú |
Propanone Methyl magnesium ê ú
bromide êë CH3 úû CH3
2-Methyl propan -2-ol
H+
(iii) CH3 — CH = CH2 + H2 O ¾Markovnikov's
¾ ¾ ¾¾® CH3 — C H— CH3
addition |
Propene
OH
Propan -2-ol
25. (i) In aniline, the lone pair of electrons on N-atom are delocalised over benzene ring due to
resonance. As a result, electron density on the nitrogen atom decreases. In contrast, in
–
methylamine, +I-effect of CH3 group increases electron density on the nitrogen atom.
Therefore, aniline is a weaker base than methylamine, hence its pKb value is more than that for
methylamine.
(ii) Ethylamine is soluble in water due to formation of inter-molecular hydrogen bonds with water
molecules. However, in aniline due to large hydrophobic part, i.e., hydrocarbon part, the extent
of hydrogen bonding decreases considerably and hence aniline is insoluble in water.
(iii) Due to the presence of two H-atoms on N-atom, primary amines undergo extensive
intermolecular hydrogen bonding whereas tertiary amines have no H-atoms on the nitrogen
atom, do not undergo H-bonding. As a result, primary amines have higher boiling points than
tertiary amines.
26. (i) Name of monomer Structure
Ethene CH2 = CH2
Vinyl chloride CH2 = CH–Cl
Tetrafluoroethene F2C = CF2
27. (i) Food Preservatives: These are the chemical substances which are added to the food materials
to prevent their spoilage due to microbial growth and to retain their nutritive value for long
time. Sodium benzoate, sodium metabisulphite are some common preservatives.
Preservatives prevent rancidity and kill or inhibit the growth of microorganism.
Examination Papers 201
(ii) Synthetic Detergents: Detergents are cleansing agents which have all the properties of soaps,
but actually do not contain any soap e.g., sodium dodecylbenzene sulphonate. These can be
used both in soft and hard water as they give foam even in hard water. Detergents are mainly
classified into three categories:
(i) Anionic detergents
(ii) Cationic detergents
(iii) Non-ionic detergents
(iii) Antacids: These are the chemical substances which neutralize the excess acid and raise the pH
to an appropriate level in the stomach. Sodium hydrogen carbonate or a mixture of aluminium
and magnesium hydroxide are some common antacids.
28. (a) The lead storage battery is a secondary cell.
The cell reactions when the battery is in use are given below
At anode: Pb( s) + SO24- ( aq) ¾ ¾
¾® PbSO4 ( s) + 2e -
At cathode: PbO2 ( s) + SO24- ( aq) + 4H+ ( aq) + 2e - ¾ ¾® PbSO4 ( s) + 2H2 O(l)
Overall cell reaction: Pb( s) + PbO2 ( s) + 2H2 SO4 ( aq) ¾ ¾
¾® 2PbSO4 ( s) + 2H2 O(l)
(b) For half cell reaction
–
Cr2 O27- ( aq) + 14H+ ( aq) + 6 e ¾
¾® 2Cr 3+ ( aq) + 7H2 O (l)
o 0.0591 [Cr 3+ ] 2
Ecell = E cell - log
n [Cr2 O2–
7 ] [H ]
+ 14
M g mol -1 ´ 2A ´ 3 ´ 60 ´ 60 s
m= = 0.119 × M g
2 ´ 96500 C mol -1
m = 0.119 × M g
0.119 ´ M g
No. of moles of mercury produced = = 0.119 mol
M g mol -1
(b) At anode: Al (s) ¾
¾® Al 3+ ( aq) + 3e – ] ´ 2
At cathode: Ni 2+ + 2 e – ¾
¾® Ni (s) ]×3
(HPO3)3
OR
(a) (i) 3Cl2 + 6NaOH (conc.) ¾
¾® 5NaCl + NaClO3 + 3H2O
(Hot)
(b) (i) P
H OH
OH
Two, as the structure of H3PO4 has two P—OH bonds.
(ii) This is due to absence of d-orbitals in fluorine.
(iii) Noble gases being mono atomic gases have no interatomic forces except weak dispersion
forces, therefore they have low boiling points.
30 (a) (i) Cannizzaro reaction: Aldehydes which do not have an a-hydrogen atom undergoes
disproportionation reactions on treatment with concentrated alkali to give a mixture of
carboxylic acid salt and alcohol.
+
2 HCHO ¾Conc.
¾¾ NaOH
¾
¾® HCOO Na + CH3 - OH
Formaldehyde Sod.formate Methyl alcohol
(ii) Clemmensen reduction: The carbonyl group of aldehydes and ketones is reduced to CH2
group on treatment with zinc-amalgam and concentrated hydrochloric acid.
> C = O + 4(H) ¾Zn ¾– Hg
¾® > CH2 + H2 O
Aldehyde HCl (conc.)
or
Ketone
OH
dil. NaOH D
(b) (i) CH3CHO CH3CH—CH2CHO CH3CH—CHCHO
Ethanal But-2-enal
CrO3 – H 2 SO4
(ii) CH3 CH2 CH2 CH2 OH ¾ ¾ ¾ ¾ ¾® CH3 CH2 CH2 COOH
Butan – l – ol Butanoic acid
–+
CH2CH3 COOK COOH
KMnO4–KOH H3O+
(iii)
D
OR
(a) (i) Benzoic acid on warming with sodium hydrogen carbonate gives brisk effervescence of
CO2 gas while ethyl benzoate does not respond to this test
– +
C6H5COOH + NaHCO3 ¾
¾® C 6 H5– CO O Na + CO2 + H2 O
Benzoic acid Brisk
effervescence
204 Xam idea Chemistry—XII
COOH COCl
SOCl2 +SO2+HCl
(b) (i)
COOH heat COCl
(i) B2H6,H2O2/OH
(iii) CH2 CHO
(ii) PCC
9. (i) Unit cell: A unit cell is the smallest portion of a crystal lattice which, when repeated in
different direction, generates the entire lattice.
(ii) Coordination number: The number of nearest neighbours of any constituent particle in a
packing is called its coordination number. The coordination number of an atom in the bcc
structure is 8.
12. Consider the reaction nR ¾ ¾® Products
As the reaction is of second order
\ Rate, r = k [R]2 ...(i)
If the concentration of the reactant reduced to half, then
2
éRù
Rate, r ¢ = kê ú ...(ii)
ë2û
Examination Papers 205
22. (i)
en en
en en
Co Co
en en
d-Tris-(ethane1,2-diamine) l-Tris-(ethane1,2-diamine)
cobalt (III) cobalt (III)
Pt Pt
Cl NH3 H3N Cl
cis-Diamminedichloro trans-Diamminedichloro
platinum (II) platinum (II)
(iii) NH3 + Cl +
Fe Fe
cis-Tetraamminedichloro trans-Tetraamminedichloro
iron (III) iron (III)
11. Molarity is the number of moles of solute dissolved in one litre of solution whereas molality is the
number of moles of solute per kilogram of the solvent. Molarity decreases with increase in
temperature as volume increases with increase in temperature. Molality is independent of temperature
because mass does not depend on temperature.
14. (i) Pig iron is melt with scrap iron and coke using hot air blast. Due to this, impurities such as C, S
and P present in the pig iron are removed as CO2, SO2 and P2O5 and carbon content reduced to
about 3%.
(ii) Bauxite is soluble in concentrated NaOH solution whereas impurities are not.
15. (i) This is due to presence of unpaired electrons in the (n–1) d orbitals of transition elements.
(ii) The chemistry of actinoids is not as smooth as lanthanoid because they are radioactive and
show greater number of oxidation states due comparable energies of 5f, 6d and 7s orbitals.
18. The following facts and reactions cannot be explained by open chain structure of glucose.
(i) Despite having the aldehyde group, glucose does not give 2, 4-DNP test, Shiff’s test and it does
not form the hydrogen sulphite addition product with NaHSO3.
(ii) The penta-acetate of glucose does not react with hydroxylamine indicating the absence of free
aldehydic group.
21. (i) This is because bond dissociation energy of F2 is lower than Cl2 Moreover, fluorine forms
stronger bond with nitrogen due to comparable size.
(ii) The acidic strength of compounds increases because of increase in polarity of E—H bond from
P—H to H—Cl, which is due to increase in electronegativity of E.
(iii) In SF6, S atom is sterically protected by six F atoms and does not allow water molecules to
attack the S atom. Further, F does not have d-orbitals to accept the electrons denoted by H2O
molecules. Due to these reasons, SF6 is kinetically an inert substance.
22.
CH CH2
26. —CH—CH—
(i) CH2— —CH and
2
Buta-1, 3-diene
Styrene
208 Xam idea Chemistry—XII
COOH
COOH
Terephthalic acid
21. State the principle on which each of the following processes operates:
(i) Recovery of silver after the silver ore has been leached with NaCN.
(ii) Electrolytic refining of a metal.
(iii) Vapour phase refining of a metal.
22. Complete the following chemical equations:
(i) NaOH + Cl 2 ¾ ¾®
(hot and conc.)
23. (a) Mention the optimum conditions for the industrial manufacture of ammonia by Haber’s process.
(b) Explain the following giving appropriate reasons:
(i) Sulphur vapour exhibits paramagnetic behaviour.
(ii) Red phosphorus is less reactive than white phosphorus.
OR
Draw the structures of the following molecules:
(i) NF3 (ii) H2S2O8 (iii) H3PO3
Examination Papers 211
H
(ii) + HBr ¾
¾®
H H
(iii) CH3CH2CH — CH2 + HBr ¾
¾®
25. Illustrate the following reactions giving a chemical equation in each case:
(i) Gabriel phthalimide synthesis
(ii) A coupling reaction
(iii) Hoffmann’s bromamide reaction
26. How would you obtain
(i) Benzoquinone from phenol?
(ii) Propan-2-ol from propene?
(iii) 2-Methylpropan-2-ol from methyl magnesium bromide?
27. Mention two important uses for each of the following polymers:
(i) Bakelite (ii) Nylon 6,6 (iii) PVC
28. (a) Express clearly what you understand by ‘rate expression’ and ‘rate constant’ of a reaction.
(b) Nitrogen pentoxide decomposes according to the equation
2N2 O5 ( g) ¾
¾® 4NO2 ( g) + O2 ( g)
This first order reaction was allowed to proceed at 40°C and the data given below were
collected:
[N2O5](M) Time (min)
0.400 0.00
0.289 20.00
0.209 40.00
0.151 60.00
0.109 80.00
(i) Calculate the rate constant for the reaction. Include units with your answer.
(ii) Calculate the initial rate of reaction.
(iii) After how many minutes will [N2O5] be equal to 0.350 M?
OR
(a) Define
(i) Order of a reaction.
(ii) Elementary step in a reaction
(b) A first order reaction has a rate constant value of 0.00510 min–1.
If we begin with 0.10 M concentration of the reactant, how much of the reactant will remain
after 3.0 hours?
212 Xam idea Chemistry—XII
(i) ¾KMnO
¾¾ ¾ 4
®
KOH, Heat
COOH
(ii) ¾SOCI
¾¾ 2
®
Heat
COOH
H O+
(iii) C6H5CONH2 3¾
¾¾ ¾®
heat
Examination Papers 213
27. (a) What does the designation ‘6,6’ in nylon 6, 6 polymer mean?
(b) Which polymer is obtained when free radical polymerisation of chloroprene occurs? Write the
structure of the polymer thus obtained.
Solutions
CBSE (Foreign) SET–I
1. Pure substances exhibiting conductivity similar to that of silicon and germanium are called intrinsic
semiconductors.
2. Henry’s law: It states that the partial pressure of a gas in vapour phase (P) is proportional to its mole
fraction (x) in the solution.
3. Denticity: The number of coordinating groups present in ligand is called the denticity of ligand. For
example, bidentate ligand ethane-1, 2-diamine has two donor nitrogen atoms which can link to central
metal atom.
·· ··
H2 N— CH2 — CH2 — N H2
Ethane–1, 2–diamine
4. 1–Bromopentane, as it is a primary alkyl halide.
5. 2–Bromo –3– methyl-but –2–en–1–ol.
O O
|| ||
6. CH3 — CH2 — C— CH2 — C — H
Examination Papers 215
H H
| |
7. R ® N·· + H+ l R — N+ — H
| |
H H
Due to +I effect alkyl group pushes electron towards nitrogen and thus makes the lone pair of electrons
more available for sharing with the proton of the acid. Hence alkyl amine is more basic than ammonia.
8. The antibiotic which is effective against a wide range of microorganisms is known as broad spectrum
antibiotic. For example, chlorophenicol.
9. Molarity (M) is the number of moles of solute dissolved in one litre of solution whereas molality (m)
is the number of moles of the solute per thousand grams of solvent.
If MB is the molar mass of solute, d is the density of solution then molarity (M) value of a solution can
be converted into its molality (m) by using the following for formula.
1000 ´ M
m=
1000 ´ d - M ´ M B
10. DTf = K f ´ m
Kf = 1.86°C kg mol–1, m = 0.561 mol kg–1
Substituting these values in the above equation,
We get,
DTf = 1.86 oC kg mol–1 × 0.561 mol kg–1 = 1.04oC
(DTf ) Calculated = 1.04 °C, (DTf) Observed = 2.93 °C
Observed colligative property ( DTf ) observed
i= =
Calculated colligative property ( DTf ) calculated
2.93 o C
i= = 2.82.
1.04 o C
11. Ni(s) + 2Ag+(aq) ¾¾® Ni2+ (aq) + 2Ag(s); E° = 1.05 V
Here, n = 2
n o
log Kc = E cell
0.059
2
log Kc = ´ 1.05 = 39.5932
0 . 059
Kc = antilog 39.5932 = 3.919 × 1039
Kc = 3.92 × 1039
DG o = – nFE cell
o
13. (i) Production of Vacuum: Adsorption can be successfully applied to create conditions of high
vacuum. For this a bulb of charcoal cooled in liquid air, is connected to vessel which has
already been exhausted as far as possible by vacuum pump. The remaining traces of air inspite
of low pressure are adsorbed by the charcoal almost completely.
(ii) Heterogeneous Catalysis: There are many gaseous reactions of industrial importance
involving solid catalyst. Manufacture of ammonia using iron as a catalyst, manufacture of
H2SO4 by contact process using V2O5 catalyst and use of finely divided nickel in the
hydrogenation of vegetable oils are the excellent examples. The gaseous reactants are adsorbed
on the surface of the solid catalyst. As a result, the concentration of the reactants increases on
the surface of the catalyst and hence the rate of reaction increases.
14. (i) Larger the difference in electronegativity greater will be polarity and hence greater will be
acidic character.
(ii) As HClO4 is most stable and tendency to give oxygen is least while HClO is least-stable and
gives oxygen most easily.
15. (i) Dichloridobis - (ethane–1, 2–diamine) cobalt (III) chloride
Cl + Cl +
Cl
en
Co en Co en
en Cl
Octahedral Octahedral
+
cis-[CoCl2 (en)2 ]
+ trans-[CoCl2 (en)2 ]
Pt
O2N NH3
Cl
Tetrahedral
O
||
16. (i) Peptide linkage: The amide (— C— NH—) linkage between two a-amino acids formed with
the loss of a water molecule is called a peptide linkage.
(ii) The six membered cyclic structure of glucose is called pyranose structure ( a - or b -), in
analogy with heterocylic compound pyran.
Examination Papers 217
CH2OH
H O H
H
OH H
HO OH
H OH
a – D – (+) – Glucopyranose
+
17. H
(i) C12H22O11 + H2O ¾ ¾¾® C6H12O6 + C6H12O6
or invertase
Sucrose Glucose Fructose
+
H
(ii) C12H22O11 + H2O ¾ ¾¾® C6H12O6 + C6H12O6
or Lactase
Lactose Glucose Galactose
OR
The following facts and reactions cannot be explained by open chain structure of glucose.
(i) Despite having the aldehyde group, glucose does give 2, 4-DNP test, Shiff’s test and it does not
form the hydrogen sulphite addition product with NaHSO3.
(ii) The penta-acetate of glucose does not react with hydroxylamine indicating the absence of free
aldehydic group.
18. (i) Hard water contains calcium and magnesium salts. In hard water, soaps get precipitated as
calcium and magnesium soaps which being insoluble stick to the clothes as gummy mass.
(ii) As synthetic detergents can be used in hard water as well as acidic solutions.
19. (i) For fcc (or ccp), a = 2 2r = 2 × 1.414 × 125 pm
= 354 pm
(ii) a = 354 pm = 3.54 × 10–8 cm
Volume of one unit cell = a3 = (3.54× 10–8 cm)3 = 4.436 × 10–23cm3 = 4.44 cm3
Total volume
Number of unit cells =
Volume of one unit cell
1 cm 3
= -23 3
= 2.25 × 1022
4.44 ´ 10 cm
23. (a) Optimum conditions for the industrial manufacture of ammonia by Haber’s process.
Pressure: 200 bar
Temperature: 723–773 K
Catalyst: Finely divided iron and molybdenum as promoter.
(b) (i) In vapour state sulphur partly exists as S2 molecule which has two unpaired electrons in
the antibonding p* molecular orbitals like O2 and, hence exhibits paramagnetic behaviour.
Examination Papers 219
(ii) White phosphorus is more reactive than red phosphorus due to its discrete tetrahedral
structure and angular strain. Red phosphorus is less reactive due its polymeric structure.
OR
(i) Total no. of electron pairs around
1
The central N atom = (5 + 3) = 4
2
N
No. of bond pairs = 3 F F
No. of lone pairs = 1
Therefore, according to VSEPR theory; NF3 should be pyramidal.
F
O O O
(ii) S S P
O O O O H OH
OH OH OH
Peroxodisulphuric acid Orthophosphorous acid
(H2S2O8) (H3PO3)
H
(ii) + HBr CH — CH3
H H
Br
O
½½
¾ COOH ¾C
H 2 O/ H +
+ R ¾ NH2 ¬¾¾¾¾¾ N¾ R
¾ COOH 1 ° amine ¾C
½½
Phthalic acid
O
(ii) Coupling reactions:
Diazonium salts react with aromatic amines in weakly acidic medium and phenols in weakly
alkaline medium to form coloured compounds called azo dyes by coupling at p-position of
amines or phenol. The mechanism is basically that of electrophilic aromatic substitutions where
the diazonium ion is electrophile.
+ - OH
¾ N º N Cl + H ¾ ¾ OH ¾¾¾¾¾®
(pH 9-10)
Phenol
¾ N = N¾ ¾ OH + Cl - + H2 O
p -Hydroxy -azobenzene
(orange dye)
+ - H+
¾ N º N Cl + H ¾ ¾ NH2 ¾¾¾¾¾®
(pH 4 -5)
Aniline
¾ N = N¾ ¾ NH2 + Cl - + H2 O
p -Amino azobenzene
(yellow dye)
Benzamide Aniline
OH O
Na2Cr2O7/H2SO4
26. (i)
Phenol
O
Benzoquinone
Examination Papers 221
H+
(ii) CH3 — CH = CH2 + H2 O ¾Markovnikov's
¾ ¾ ¾¾® CH3 — C H— CH3
addition |
Propene
OH
Propan -2-ol
O é OMgBr ù OH
|| ê | ú |
(iii) CH3 — C— CH3 + CH3 MgBr ¾¾® êCH3 — C— CH3 ú ¾H¾
2O
¾ ® CH3 — C— CH3
ê | ú |
Propanone Methyl magnesium ê ú
bromide êë CH3 úû CH3
2-methyl propan -2-ol
27. (i) It is used for making combs, fountain pen barrels, phonograph records.
It is used widely in making electrical goods such as switches, plugs, handles of various utensils.
(ii) It is used in making bristles for brushes, ropes.
It is used for making carpets and fabrics in textile industry.
(iii) It is used in the manufacture of rain coats, hand bags, water pipes, vinyl flooring.
It is used for insulating electric wires.
28. (a) An experimentally determined expression which relates the rate of reaction with the
concentration of reactants is called rate law while the rate of reaction when concentration of
each reactant is unity in a rate law expression is called rate constant.
(i) Comparing power of mole in L–1 mol s–1 and (mol L–1)1–n s–1,
We get
1=l–n Þ n = 0 i.e., zero order reaction
(ii) Again comparing power of mole in L mol–1s–1 and (mol L–1) 1–n s–1, we get
–1 = 1 – n Þ n = 2, i.e., second order reaction
–1
(b) (i) When t = 20 min, [A] = 0.289 mol L
Also, [A]0 = 0.400 mol L–1
For a first order reaction
2.303 [A] °
k= log
t [A]
2.303 0.400
\ k= log
20 0.289
2.303 4.00
Þ k= log
20 2.89
2.303
Þ k= [log 4.00 – log 2.89]
20
2.303
Þ k= [0.6021 – 0.4609]
20
2.303
Þ k= ´ 01412
.
20
Þ k = 2.303 × 0.00706 = 0.016259 min–1
Þ k = 1.6259 × 10–2 min–1
222 Xam idea Chemistry—XII
(b) (i) The catalytic activity of transition metals and their compounds is attributed to the
following reasons:
Because of their variable oxidation states transition metals form unstable intermediate
compounds and provide a new path with lower activation for the reaction.
In some cases, the transition metal provides a suitable large surface area with free
valencies on which reactants are adsorbed.
In general in the same group of d block elements, the 4d and 5d transition element has
larger size than that of 3d elements. Thus, the valence electrons are less lightly held and
hence can form metal-metal bond more frequently.
(ii) Mn3+ is less stable and changes to Mn2+ which is more stable due to half filled d-orbital
configuration. That is why, Mn3+ undergoes disproportionation reaction.
(iii) Co (III) has electric configuration 3d, 4s, i.e., it has three unpaired electron. In the
presence of strong ligands, two unpaired electrons in 3d subshell pair up and third
unpaired electron shift to higher energy subshell from where it can be easily lost and
hence oxidised to Co(III).
OR
3+ – 2+
(a) (i) 2Fe + 2I ¾ ¾® 2Fe + I2
(ii) 2CrO4 + 2H+ ¾
2–
¾® Cr2 O2– 7 + H2 O
(b) (i) In aqueous solution Cu+ undergoes disproportionation to form a more stable Cu2+ ion.
2 Cu+ (aq) ¾ ¾® 2 Cu2+(aq) + Cu(s)
The higher stability of Cu2+ in aqueous solution may be attributed to its greater negative
D hydH° than that of Cu+. It compensates the second ionization enthalpy of Cu involved in
the formation of Cu2+ ions.
(ii) Cr2+ is reducing as its configuration changes from d4 to d3, a more stable half filled t2g
configuration while Mn3+ is oxidising as Mn3+ to Mn2+results a more stable half filled d5
configuration.
(iii) The catalytic activity of transition metals and their compounds is attributed to the
following reasons:
Because of their variable oxidation states transition metals form unstable intermediate
compounds and provide a new path with lower activation for the reaction.
In some cases, the transition metal provides a suitable large surface area with free
valencies on which reactants are adsorbed.
30. (a) (i) Propanal and propanone
Tollen’s reagent test: Propanal being an aldehyde reduces Tollen’s reagent to silver
mirror but propanone being a ketone does not.
— –
CH3CH2CHO + 2[Ag(NH3)2]+ + 3OH ¾
¾® CH3 CH2 COO + 2Ag ¯ + 4NH3 + 2H2 O
Silver Mirror
Propanal
CH3COCH3 ¾Tollen's
¾ ¾® No silver mirror
reagent
C 6 H5 COCH3 + 3NaOI ¾
¾® C 6 H5 COONa + CHI 3 ¯ + 2NaOH
Acetophenone Iodoform
(Yellow ppt.)
OH
dil. NaOH D
(b) (i) CH3CHO CH3CH—CH2CHO CH3CH—CHCHO
Ethanal But-2-enal
CrO3 – H 2 SO4
(ii) CH3 CH2 CH2 CH2 OH ¾ ¾ ¾ ¾ ¾® CH3 CH2 CH2 COOH
Butan – l – ol Butanoic acid
–+
CH2CH3 COOK COOH
KMnO4–KOH H3O+
(iii)
D
OR
(a) (i) Cannizzaro reaction: Aldehydes which do not have an a-hydrogen atom undergoes
disproportionation reactions on treatment with concentrated alkali to give a mixture of
carboxylic acid salt and alcohol.
+
2 HCHO ¾Conc.
¾¾ NaOH
¾
¾® HCOO Na + CH3 - OH
Formaldehyde Sod.formate Methyl alcohol
(ii) Decarboxylation: Carboxylic acids lose carbon dioxide to form hydrocarbons when their
sodium salts are heated with sodalime.
– –
RCOO Na ¾NaOH
¾ ¾and¾CaO
¾® RH + Na 2 CO3
D
–+
CH2CH3 COOK
(b) (i) KMnO4
KOH, heat
Ethyl benzene Pot. benzoate
COOH COCl
SOCl2
(ii)
COOH heat COCl
Phthalic acid Phthaloyl chloride
H O+
3¾®
(iii) C6H5CONH2 ¾¾ C6H5COOH + NH3
heat
2. Henry’s law : It states that “the partial pressure of the gas in vapour phase ( p) is proportional to the
mole fraction of the gas ( x ) in the solution” and is expressed as
p = KH x
where, KH is the Henry’s law constant.
Significance of KH. Higher the value of Henry’s law constant KH, the lower is the solubility of the gas
in the liquid.
3. Because CO has p bonds.
8. Chemical substances which prevent the growth of microorganisms or kill them but are not harmful to
living tissues are called antiseptics.
For example, Dettol, Savlon, etc.
12.
Chemisorption Physisorption
It arises due to chemical bond formation. It arises because of van der waals’ forces.
It is irreversible in nature. It is reversible.
It is highly specific in nature. It is not specific in nature.
It results into unimolecular layers on adsorbent It results into multimolecular layers on adsorbent
surface. surface under high pressure.
16. Primary structure refers to the sequence in which various amino acids are arranged in a protein while
secondary structure refers to the shape in which a long polypeptide chain can exist as a result of
O
||
regular folding of the backbone of the polypeptide chain due to hydrogen bonding between — C—
and —NH—groups of the peptide bond.
17. (i) Geometrical isomers of [Cr(NH3)4Cl2]+
Cl + Cl +
Cr Cr
cis-Tetraamminedichlorido trans-Tetraamminedichlorido
chromium (III) ion chromium (III) ion
en en
en en
Co Co
en en
dextro-Tris-(ethane-1,2,-diamine) laevo-Tris-(ethane-1,2-diamine)
cobalt (III) ion cobalt (III) ion
18. (i) Antacids: These are the chemical substances which neutralize the excess acid and raise the pH
to an appropriate level in the stomach. Sodium hydrogen carbonate or a mixture of aluminium
and magnesium hydroxide are some common antacids.
(ii) Detergents: Detergents are cleansing agents which have all the properties of soaps, but actually
do not contain any soap, e.g., sodium dodecylbenzene sulphonate. These can be used both in
soft and hard water as they give foam even in hard water. Detergents are mainly classified into
three categories:
(a) Anionic detergents
(b) Cationic detergents
(c) Non-ionic detergents
21. (i) Leaching of bauxite ore to prepare pure alumina:
Al2O3(s) + 2NaOH(aq) + 3H2O(l) ¾ ¾® 2Na[Al (OH)4] (aq)
2Na[Al(OH)4](aq) + CO2(g) ¾ ¾® Al2O3.xH2O(s) + 2NaHCO3 (aq)
1470K
Al2O3.xH2O(s) ¾ ¾¾® Al2O3(s) + xH2O(g)
(ii) Refining of zirconium by van Arkel method.
Zr(s) + 2I2(g) ¾870K
¾¾® ZrI4 (g)
(impure)
2075 K
ZrI4 (g) ¾Tungsten
¾¾¾ ¾¾® Zr(s) + 2I 2
filament
(Pure)
27. (a) In nylon-6, 6 both the monomers hexamethylene diamine and adipic acid contain six carbon
atoms each.
(b) Neoprene is obtained by free radical polymerisation of chloroprene.
CH2 = C - CH = CH2 ¾O¾
2 peroxide
¾ ¾® —[CH2 - C = CH - CH2 —
]n
| or O2 |
Cl Cl
Chloroprene Neoprene
OH O
Na2Cr2O7/H2SO4
26. (i)
Phenol
O
Benzoquinone
H+
(ii) CH3 — CH = CH2 + H2 O ¾Markovnikov's
¾ ¾ ¾¾® CH3 — C H— CH3
addition |
Propene
OH
Propan -2-ol
O é OMgBr ù OH
|| ê | ú |
(iii) CH3 — C— CH3 + CH3 MgBr ¾¾® êCH3 — C— CH3 ú ¾H¾
2O
¾ ® CH3 — C— CH3
ê | ú |
Propanone Methyl magnesium ê ú
bromide êë CH 3 úû CH3
2-mehtyl propan -2-ol
27. Polymers which are formed by the repeated addition of monomers molecules possessing double or
triple bonds are called the addition polymers.
The two types of addition polymers are:
(i) Homopolymers: The addition polymers formed by the polymerisation of a single monomeric
species are called homopolymers, e.g., polyethene.
n CH2 — CH2 ¾ ¾® —(CH2 — CH2 — )n
Ethene Polyethene
(ii) Copolymers: The polymers made by addition polymerisation from two different monomers are
known as copolymers. e.g., Buna-s.
CH CH2 (CH2—CH2—CH—CH2—CH—CH2)n
11. Name the two groups into which phenomenon of catalysis can be divided. Give an example of each
group with the chemical equation involved.
12. What is meant by coagulation of a colloidal solution? Describe briefly any three methods by which
coagulation of lyophobic sols can be carried out.
13. Describe the principle involved in each of the following processes.
(i) Mond process for refining of Nickel.
(ii) Column chromatography for purification of rare elements.
14. Explain the following giving an appropriate reason in each case.
(i) O2 and F2 both stabilise higher oxidation states of metals but O2 exceeds F2 in doing so.
(ii) Structures of Xenon fluorides cannot be explained by Valence Bond approach.
15. Complete the following chemical equations:
(i) Cr2O72– + H+ + I– ¾¾®
– – +
(ii) MnO4 + NO2 + H ¾ ¾®
16. What is meant by (i) peptide linkage (ii) biocatalysts?
17. Write any two reactions of glucose which cannot be explained by the open chain structure of glucose
molecules.
18. Draw the structure of the monomer for each of the following polymers:
(i) Nylon-6
(ii) Polypropene
19. Tungsten crystallises in body centred cubic unit cell. If the edge of the unit cell is 316.5 pm, what is
the radius of tungsten atom?
OR
Iron has a body centred cubic unit cell with a cell dimension of 286.65 pm. The density of iron is
7.874 g cm–3. Use this information to calculate Avogadro’s number. (At. mass of Fe = 55.845 u)
20. Calculate the amount of KCl which must be added to 1 kg of water so that the freezing point is
depressed by 2 K. (Kf for water = 1.86 K kg mol–1)
21. For the reaction
2NO(g) + Cl2(g) ¾ ¾® 2NOCl(g),
the following data were collected. All the measurements were taken at 263 K:
Experiment Initial [NO] (M) Initial [Cl2] (M) Initial rate of disappearance
No. of Cl2 (M/min)
1 0.15 0.15 0.60
2 0.15 0.30 1.20
3 0.30 0.15 2.40
4 0.25 0.25 ?
OR
(a) Define molar conductivity of a solution and explain how molar conductivity changes with
change in concentration of solution for a weak and a strong electrolyte.
(b) The resistance of a conductivity cell containing 0.001 M KCl solution at 298 K is 1500 W. What
is the cell constant if the conductivity of 0.001 M KCl solution at 298 K is 0.146 × 10–3 S cm–1?
232 Xam idea Chemistry—XII
(iii) ¾1.¾
CrO2 Cl 2
¾¾ +
®
2. H 3O
NO2
234 Xam idea Chemistry—XII
Solutions
CBSE (Delhi) SET–I
1. The process of addition of an appropriate amount of suitable impurity to an intrinsic semiconductor to
enhance its conductivity is called doping.
2. Graphite is used as electrodes in the electrometallurgy of aluminium. The electrode reactions are:
Cathode: Al3+ (melt) + 3e– ¾ ¾® Al(l)
2–
Anode: C(s) + O (melt) ¾ ¾® CO(g) + 2e–;
C(s) + 2O2–(melt) ¾ ¾® CO2(g) + 4e–
3. PCl4–, as phosphorus has 10 electrons which can’t be accommodated in sp3 hybrid orbitals.
4. 3-Bromo-2-methylpropene
CH3
|
5. CH3 — C— CH3
|
OH
6. Butanone < Propanone < Propanal < Ethanal
7. (CH3)2NH > CH3NH2 > (CH3)3N > NH3
8. Homopolymerisation is a polymerisation reaction in which monomers of one kind are allowed to
polymerise and form a homopolymer.
—CH2 ¾Polymerization
n CH2— ¾ ¾ ¾¾® — ( CH2—CH2 —
) n
Ethene Polyethene (Homopolymer)
H2C N C—O
(i) H C —CH2
(ii) CH3—CH—
2 CH2
H2C CH2 Propene
Caprolactum
19. a = 316.5 pm
3
For bcc unit cell, r= a
4
3
\ r=× 316.5 pm = 137.04 pm
4
OR
a = 286.65 pm = 286.65 × 10 cm; M = 55.845 g mol–1; d = 7.874 g cm–3
–10
Cl Cl
H
E
+ E
Inductive effect destabilizes the
intermediate carbocation
Cl Cl
H
+ E (Attack at ortho-position)
+ E
Cl Cl
+ (Attack at para-position)
+ E
E H
Resonance effect stabilizes the
intermediate carbocation
The negative inductive effect is stronger than resonance effect and causes net electron withdrawal and
thus causes net deactivation. The resonance effect tends to oppose the inductive effect for the attack at
ortho and para positions and hence makes the deactivation less for ortho and para attack. Thus the
electrophilic substitution takes place at ortho and para positions..
25. (i) CH3—CH2—CH2—CH2—OH ¾ ¾(O)
¾¾® CH3—CH2—CH2—COOH
CrO3 – H 2 SO4
Butan-1-ol Butanoic acid
(ii) CH3—CH—
—CH—CH2—OH ¾ ¾(O)
¾¾® CH3—CH—
—CH—CHO
PCC
But-2-enol But-2-enal
CH3 CH3
| |
(iii) CH3—CH—CH2—OH ¾ ¾(O)
¾¾® CH3—CH—COOH
CrO3 – H 2 SO4
2-Methylpropan-1-ol 2-Methylpropanoic acid
26. + –
NO2 NH2 N2Cl CN COOH
+
Sn/HCl NaNO2/HCl CuCN/KCN H2O/H
(i)
273-278 K
Nitrobenzene Benzoic acid
+ –
NH2 N2Cl CN COOH CH2OH
+
NaNO2/HCl CuCN/KCN H2O/H LiAlH4
(iii)
273-278 K
Aniline Benzyl alcohol
240 Xam idea Chemistry—XII
Alternatively,
+ –
NH2 N2Cl CH3
NaNO2/HCl H3PO2/H2O CHCl3/
273-278 K anhyd. AlCl3
Aniline
Cl2/hn
CH2OH CH2—Cl
NaOH(aq)
27. (i) Tranquilizers are a class of chemical compounds used for the treatment of stress, fatigue, and
mild or even severe mental diseases. These relieve anxiety, stress, irritability or excitement by
inducing a sense of well-being, e.g., iproniazid, chlordiazopoxide, equanil, luminal, etc.
(ii) Food preservatives are the chemical substances which are added to food materials to prevent
their spoilage due to microbial growth and to retain their nutritive value for long periods.
Preservatives prevent the rancidity of food and inhibit growth or kill the microorganisms. The
most-common preservatives used are sugar, vegetable oil, sodium benzoate, salts of ascorbic
acid and propanoic acid.
(iii) Synthetic detergents are cleansing agents, which have all the properties of soaps but actually do
not contain any soap. These can be used in both soft water and hard water as they produce foam
even in hard water. These are mainly classified into three categories:
l Anionic detergents, e.g., sodium dodecylbenzene sulphonate
28. (a) Lead storage battery is a secondary battery. The reactions occurring in lead storage battery
when current is drawn from it are:
Anode: Pb(s) + SO42–(aq) ¾ ¾® PbSO4(s) + 2e–
Cathode: PbO2(s) + SO4 (aq) + 4H+(aq) + 2e– ¾
2–
¾® PbSO4(s) + 2H2O(l)
Overall reaction: Pb(s) + PbO2(s) + 2H2SO4(aq) ¾ ¾® 2PbSO4(s) + 2H2O(l)
(b) Anode: Zn ¾ ¾® Zn2+ + 2e–
Cathode: Ag2O + H2O + 2e– ¾ ¾® 2Ag + 2OH–
= 0.80 V – (– 0.76 V)
E ocell = 1.56 V
DGo = – nF E ocell
\ DGo = – 2 × 96500 C mol–1 × 1.56 V = – 301080 J mol–1
DGo = – 301.08 kJ mol–1
Examination Papers 241
OR
(a) Molar conductivity of a solution at a given concentration is the conductance of the volume V of
the solution containing one mole of electrolyte kept between two electrodes with area of cross
section A and distance of unit length.
k ´ 1000
Lm = k ´ V =
c
where k is the conductivity and V is the volume of solution containing one mole of the
electrolyte and c is the molar concentration.
Molar conductivity increases with decrease 400
in concentration or increase in dilution as the
Weak electrolyte (CH3COOH)
number of ions as well as the mobility of
Cl F
(ii) There are three bond pairs and two lone pairs of electrons around Cl F
atom in ClF3. Therefore according to VSEPR theory, ClF3 should be
bent T-shaped. The angle F—Cl—F is less than 90°. ClF3
242 Xam idea Chemistry—XII
(iii) There are two bond pairs and three lone pairs of electrons around F
Xe atoms in XeF2. Therefore according to VSEPR theory, XeF2
should be linear. The angle F—Xe—F is greater than 90°.
Xe
OR
F
(a) (i) 6NaOH + 3Cl2 ¾
¾® 5NaCl + NaClO3 + 3H2O XeF2
(hot and conc)
(ii) XeF4 + O2F2 ¾
¾® XeF6 + O2
(b) (i) (ii) (iii)
O O O O
F F
P S S Xe
H OH O O O F F
H OH HO
H3PO2 H2S2O7 XeOF4
30. (a) (i) The carbonyl group of aldehydes and ketones is reduced to CH2 group on treatment with
zinc-amalgam and concentrated hydrochloric acid. The reaction is known as Clemmensen
reduction
Zn–Hg
C—O HCl
CH2 + H2O
Zn–Hg
CH3COCH3 + 4(H) HCl
CH3CH2CH3 + H2O
Acetone Propane
(ii) Carboxylic acids having an a-hydrogen are halogenated at the a-position on treatment
with chlorine or bromine in the presence of small amount of red phosphorus to give
a-halocarboxylic acids. This reaction is called Hell–Volhard–Zelinsky reaction.
a (i) X2/red P
R—CH2—COOH R—CH—COOH (X = Cl, Br)
(ii) H3O+
Carboxylic acid X
a-Halocarboxylic acid
K2Cr2O7/H2SO4 HNO2
CH3COOH CH3CH2OH CH3CH2NH2
Ethanoic acid
OR
(a) (i) When aldol condensation is carried out between two different aldehydes and/or ketones, it
is called cross aldol condensation.
O O – O
OH
C—H + C—CH3 293 K CH—CH—C—
Benzaldehyde Benzalacetophenone
(Major product)
(ii) Sodium salt of carboxylic acids on heating with soda lime lose carbon dioxide and form
hydrocarbons. This reaction is called decarboxylation.
– +
R — CO O Na ¾NaOH¾ ¾and
¾CaO
¾® R — H + Na 2 CO3
Sodium carboxylate D Hydrocarbon
(b) (i) Pentan-2-one when treated with NaOI (I2/NaOH) gives yellow precipitate of iodoform
but pentan-3-one does not give this test.
CH3—CH2—CH2—COCH3 + 3NaOI ¾ ¾® CH3CH2CH2COONa + CHI3 ¯ + 2NaOH
Pentan-2-one Sodium Iodoform
hypoiodite (Yellow ppt.)
(ii) Benzaldehyde being an aldehyde gives silver mirror with Tollen’s reagent but
acetophenone being a ketone does not give this test.
C6H6CHO + 2[Ag(NH3)2]+ + 3OH– ¾ ¾® C6H5COO– + 2Ag¯ + 4NH3 + 2H2O
Benzaldehyde Tollen’s reagent Silver mirror
(iii) Benzoic acid produces brisk effervescence with sodium bicarbonate solution while phenol
does not.
C6H5COOH + NaHCO3 ¾ ¾® C6H5COONa + CO2 + H2O
Benzoic acid Sodium
bicarbonate
(ii) When nickel is heated with carbon monoxide it forms a volatile compound tetracarbonyl nickel,
Ni(CO)4 which on further heating at higher temperature decomposes to give pure nickel.
Ni + 4CO ¾330 ¾–¾¾350 K
® Ni(CO)4; Ni(CO)4 ¾450¾–¾¾470 K
® Ni + 4CO
Impure nickel Pure nickel
244 Xam idea Chemistry—XII
Square planar
Ni in [Ni(CN)4]2– geometry
CN CN CN CN
sp2 hybridization
23. (i) Cr2+ is a reducing agent as its configuration changes from d4 to d3, the later having a half-filled
t2g level. On the other hand, the change from Mn3+ to Mn2+ results in the extra stable half-filled (d5)
configuration and hence Mn3+ is an oxidizing agent.
(ii) This is due to very small energy gaps between 5f, 6d and 7s subshells in actinoids.
(iii) In aqueous solutions, the transition metal ions which have partially filled d-orbitals undergo d-d
transition by absorbing light from visible region and radiate complementary colour.
Examination Papers 245
2-ethyl benzaldehyde
The reactions involved in the question are:
NO2 NO2
CHO + N2NHN NO2 CH—NHN NO2
CH2CH3 CH2CH3
2-Ethylbenzaldehyde 2, 4-DNP 2, 4-DNP derivative
–
OH
2 CHO COO– + CH2OH
CH2CH3 CH2CH3 CH2CH3
+
KMnO4/KOH H 3O
CHO COO– COOH
–
CH2CH3 COO COOH
2-Ethyl benzaldehyde 1, 2-Benzenedicarboxylic acid
OR
(a) (i) Phenol gives a violet colouration with neutral FeCl3 solution while benzoic acid gives buff
coloured precipitate of ferric benzoate.
6C6H5OH + FeCl3 ¾ ¾® [Fe(OC6H5)6]3– + 3H+ + 3HCl
Violet complex
3C6H5COOH + FeCl3 ¾
¾® (C6H5COO)3Fe + 3HCl
Benzoic acid Buff coloured ppt.
246 Xam idea Chemistry—XII
(ii) Acetophenone being a methyl ketone when treated with NaOI(I2/NaOH) gives yellow
precipitate of iodoform while benzophenone does not give this test.
C6H5COCH3 + 3NaOI ¾ ¾® C6H5COONa + CHI3 + 2NaOH
Acetophenone Sodium benzoate Iodoform
(Yellow ppt.)
O
CHO
C O
(b) (i) C6H5 (ii) CH3—C—CH3 (iii)
5. CH3—CH2—CH2—CH—CH—
—CH2
|
OH
20. DTf = 0°C – (– 0.34 °C) = 0.34 °C or 0.34 K
WB = 15.0 g; WA = 450 g; Kf = 1.86 K kg mol–1
Substituting these values in the expression,
K f ´ WB ´ 1000
MB = , we get
DTf ´ WA
(b) (i) This is because in NH3 nitrogen is more electronegative than hydrogen while in NF3,
nitrogen is less electronegative than fluorine.
Cl
(ii) In gaseous and liquid phases PCl5 has a trigonal bipyramidal
Cl
240 pm
Cl
(iii) In vapour state sulphur partly exists as S2 molecule which has two unpaired electrons in
the antibonding p* orbitals like O2 and hence it exhibits paramagnetism.
248 Xam idea Chemistry—XII
OR
(a) (i) XeF4 + SbF5 ¾ ¾® [XeF3] [SbF6]–
+
26. What is essentially the difference between a-glucose and b-glucose? What is meant by pyranose
structure of glucose?
27. Differentiate between thermoplastic and thermosetting polymers. Give one example of each.
28. (a) Define the following terms:
(i) Mole fraction (ii) Ideal solution
(b) 15.0 g of an unknown molecular material is dissolved in 450 g of water. The resulting solution
freezes at – 0.34°C. What is the molar mass of the material? (Kf for water = 1.86 K kg mol–1)
OR
(a) Explain the following:
(i) Henry’s law about dissolution of a gas in a liquid.
(ii) Boiling point elevation constant for a solvent.
(b) A solution of glycerol (C3H8O3) in water was prepared by dissolving some glycerol in 500 g of
water. This solution has a boiling point of 100.42°C. What mass of glycerol was dissolved to
make this solution? (Kb for water = 0.512 K kg mol–1)
29. (a) Draw the molecular structures of the following compounds
(i) N2O5 (ii) XeOF4
(b) Explain the following observations:
( i) Sulphur has a greater tendency for catenation than oxygen.
(ii) ICl is more reactive than I2.
(iii) Despite lower value of its electron gain enthalpy with negative sign, fluorine (F2) is a
stronger oxidising agent than Cl2.
OR
(a) Complete the following chemical equations:
(i) Cu + HNO3 (dilute) ¾ ¾®
(ii) XeF4 + O2F2 ¾ ¾®
(b) Explain the following observations:
(i) Phosphorus has a greater tendency for catenation than nitrogen.
(ii) Oxygen is a gas but sulphur a solid.
(iii) The halogens are coloured.
30. (a) Write a suitable chemical equation to complete each of the following transformations:
(i) Butan-1-ol to butanoic acid
(ii) 4-Methylacetophenone to benzene-1, 4-dicarboxlylic acid.
252 Xam idea Chemistry—XII
(b) An organic compound with molecular formula C9H10O forms 2,4-DNP derivative, reduces
Tollen’s reagent and undergoes Cannizzaro’s reaction. On vigorous oxidation it gives
1,2-benzenedicarboxylic acid. Identify the compound.
OR
(a) Give chemical tests to distinguish between
(i) Propanol and propanone
(ii) Benzaldehyde and acetophenone
(b) Arrange the following compounds in increasing order of their property as indicated:
(i) Acetaldehyde, Acetone, Methyl tert-butyl ketone (reactivity towards HCN)
(ii) Benzoic acid, 3,4-Dinitrobenzoic acid, 4-Methoxybenzoic acid (acid strength)
(iii) CH3CH2CH(Br)COOH, CH3CH(Br)CH2COOH, (CH3)2CHCOOH (acid strength)
OR
(a) Draw the structures of the following molecules:
(i) N2O5 (ii) HClO 4
(b) Explain the following observations:
(i) H2S is more acidic than H2O.
(ii) Fluorine does not exhibit any positive oxidation state.
(iii) Helium forms no real chemical compound.
H H
H Br
7. Write a reaction which shows that all the carbon atoms in glucose are linked in a straight chain.
8. What is the cause of a feeling of depression in human beings? Name a drug which can be useful in
treating this depression.
11. Explain the role of each of the following:
(i) NaCN in the extraction of silver.
(ii) SiO2 in the extraction of copper.
18. Differentiate between disinfectants and antiseptics. Give one example of each group.
22. Write three distinct features of chemisorptions which are not found in physisorptions.
23. Explain each of the following observations:
(i) With the same d-orbital configuration (d4), Cr2+ is a reducing agent while Mn3+ is an oxidising
agent.
(ii) Actinoids exhibit a much larger number of oxidation states than the lanthanoids.
(iii) There is hardly any increase in atomic size with increasing atomic numbers in a series of
transition metals.
24. Name the following coordination entities and describe their structures:
(i) [Fe(CN)6]4– (ii) [Cr(NH3)4Cl2]+
2–
(iii) [Ni(CN)4]
(Atomic Numbers Fe = 26, Cr = 24, Ni = 28)
26. Define the following as related to proteins:
(i) Peptide linkage
(ii) Primary structure
(iii) Denaturation
254 Xam idea Chemistry—XII
Solutions
CBSE (All India) SET–I
1. The conductivity is increased by adding an appropriate amount of impurity which is electron rich or
election deficient as compared to intrinsic semiconductor.
2. The process of converting a precipitate into colloidal sol by shaking it with dispersion medium in the
presence of small amount of electrolyte is called peptisation .
3. Copper is extracted by hydrometallurgy from low grade copper ores. It is leached out using acid or
bacteria. The solution containing Cu2+ ion is treated with scrap iron or H2.
Cu2+(aq) + Fe(s) ¾ ¾® Fe2+(aq) + Cu(s)
OR
Cu2+ (aq) + H2(g) ¾ ¾® Cu(s) + 2H+(aq)
4. BiH3, as BiH3 has lower bond dissociation enthalpy than SbH3.
5. The reddish brown colour of bromine is discharged.
6. Pent-2-enal
7. CHO COOH
| HNO3
|
(CHOH)4 (CHOH)4
(O)
| |
CH2—OH COOH
Glucose Saccharic acid
8. Disinfectants are applied to non-living objects whereas antiseptics are applied to living tissues.
1
9. Conductivity (k) = × Cell constant
Resistance ( R)
Conductivity ( k) ´ 1000
Molar Conductivity ( L m ) =
Molarity ( M )
OR
k ´1000 L m ´ M
Lm = =
M 1000
138.95 cm 2 mol –1 ´ 1.5 mol L–1
k= = 0.208355 cm–1
1000 cm 3 L–1
10. Rate = k[R]2
(i) If [R] is doubled, Rate = k[2R]2 = 4k[R]2 = 4 times
2
[R ] éR ù 1 2 1
(ii) If [R] is reduced to , Rate = k ê ú = k [R ] = th
2 ë2û 4 4
11. (i) Nickel is purified by vapour phase refining. In this method nickel is heated in a stream of
carbon monoxide forming a volatile complex, nickel tetracarbonyl (Ni(CO)4), which on further
heating decomposes to give pure nickel.
Examination Papers 255
+
H
14. C—C + H2O C—C
H OH
The mechanism of the reaction involves the following three steps:
(i) Protonation of alkene to form carbocation by electrophilic attack of H3O+.
+ +
H2O + H H3O ;
H H
+ +
C—C + H—O —H —C—C + H2O
15. (i) This is due to their ability to form hydrogen bonds with water molecules.
(ii) Due to —R and —I effect of —NO2 group, the electron density in the O—H bond decreases in
ortho-nitrophenol and hence the release of H+ ion becomes easy. On the other hand, due to +R
256 Xam idea Chemistry—XII
effect of the —OCH3 group, the electron density in the O—H bond in ortho-methoxyphenol
increases, thereby making the release of H+ ion difficult.
16. (i) Carbylamine reaction: Aliphatic and aromatic primary amines when heated with chloroform and
ethanolic potassium hydroxide form carbylamines or isocyanides which are foul smelling
substances. Secondary and tertiary amines do not show this reaction.
D
R—NH2 + CHCl3 + 3KOH (alc.) ¾¾ ® RNC + 3KCl + 3H2O
D
C6H5NH2 + CHCl3 + 3KOH (alc.) ¾¾® C6H5NC + 3KCl + 3H2O
Aniline Phenyl
isocyanide
(ii) Hoffmann’s bromamide reaction: When a primary acid amide is heated with bromine in an
aqueous or ethanolic solution of NaOH, a primary amine is obtained. The amine so obtained
contains one carbon less than that present in the amide.
RCONH2 + Br2 + 4NaOH ¾ ¾® R—NH2 + Na2 CO3 + 2NaBr + 2H2O
Acid amide
C6H5CONH2 + Br2 + 4NaOH ¾
¾® C6H5NH2 + Na2CO3 + 2NaBr + 2H2O
Benzamide Aniline
Br
Aniline 2,4,6-Tribromoaniline
18. Food preservatives are the chemical substances which are added to food materials to prevent their
spoilage and to retain their nutritive value for long periods. Preservatives prevent the rancidity of food
and inhibit the growth of or kill the microorganisms. Two such substances are sodium benzoate and
salts of ascorbic acid.
19. For fcc, a = 2 2r
\ a = 2 2 × 127.8 pm = 361.4 pm = 361.4 × 10–10 cm
Here, z = 4; M = 63.55 g mol–1; a = 3.614 × 10–8 cm; NA = 6.02 × 1023 mol –1
Substituting the values in the expression,
z´ M
d= 3 , we get
a ´ NA
4 ´ 63.55 g mol –1
d= –8 3 23 –1
= 8.95 g cm–3
(3.614 ´ 10 cm) ´ 6.02 ´ 10 mol
OR
–1 –3
Here, z = 2, M = 56 g mol , d = 7.87 g cm
a = 286.65 pm = 286 .65 × 10–10cm = 2.8
Substituting the values in the expression,
Examination Papers 257
z´ M
NA = , we get
a3 ´ d
2 ´ 56 g mol –1
NA =
( 286.65 ´ 10 -10 cm) 3 ´ 7.87 g cm –3
= 6.042 × 1023 mol–1
2
æ1 ö
20. A = pr 2 = 3.14 × ç cm ÷ = 0.785 cm2; l = 50 cm
è2 ø
R ´ A 5.55 ´ 10 3 ohm ´ 0.785cm 2
Resistivity = r = = = 87.135 ohm cm
l 50 cm
1 1
Conductivity = k = = = 0.01148 s cm–1
r 87.135 ohm cm
k ´ 1000 0.01148 s cm –1 ´ 1000 cm 3 L–1
Molar Conductivity = L m = =
M 0.05 mol L–1
= 229. 6 s cm2 mol–1
21 N2 + O2 ¾ ¾® 2NO
Initial conc. in mol L–1 0.8 0.2 0
Change in conc. in mol L–1 –x –x +2x
–1
Equilibrium conc. in mol L 0.8–x 0.2 – x 2x
2
[NO] ( 2x ) 2
KC = \ 1 × 10–5 =
[N2 ][O2 ] ( 0.8 - x ) ( 0.2 - x )
As x << 0.2, therefore 0.8 – x » 0.8 and 0.2 – x » 0.2
4x 2
\ 1 × 10–5 = Þ 4x2 = 16 × 10–7
016
.
x = 6.324 × 10–4 mol L–1,
2x = 2 × 6.324 × 10–4 = 12.648 × 10–4 mol L–1
Thus at equilibrium
[N2] = 0.8 mol L–1, [O2] = 0.2 mol L–1 and [NO] = 1.265 × 10–3 mol L–1
22. (i) A colloidal system in which dispersion medium is gas and dispersed phase is either solid or
liquid is called aerosol, e.g., smoke, fog, etc.
(ii) An emulsion is a colloidal system in which both the dispersed phase and the dispersion medium
are liquids, e.g., milk, cod liver oil, etc.
(iii) There are some substances such as soap which at low concentration behave as normal
electrolytes, but at higher concentration exhibit colloidal behaviour due to the formation of
aggregates. The aggregated particles thus formed are known as micelles or associated colloids.
23. (i) Lanthanoid metals show +2 and +4 oxidation states to attain extra stable f 0 and f 7 configurations.
(ii) The main reason for positive E°(0.34 V) value for copper is that the sum of enthalpies for
sublimation and ionisation is not balanced by hydration enthalpy.
258 Xam idea Chemistry—XII
(iii) This is due to lanthanoid contraction which arises due to filling of 4 f-orbitals which have poor
shielding effect.
24. (i) [CO(en)2Cl2]+ : Dichloride bis (ethane-1,2-diamine) cobalt (III) ion
Cl + Cl + Cl +
Cl Cl
en en
Co en Co Co en
en
Cl en
trans cis
Optical isomers
Geometrical isomers
OX
Cr Cr
OX
OX OX
dextro mirror laevo
Cl NH 3 NH 3 Cl
Co Co
Cl NH 3 Cl Cl
Cl NH 3
cis-or-fac-isomer trans-or mer-isomer
25. (i) Chiral molecules (or compounds) are those molecules which are non-superimposible on their
mirror images and this property is known as chirality. Butan-2-ol is an example of chiral molecule.
+
(ii) Due to +I effect of alkyl groups the 2° carbonium ion CH3—CH—CH2—CH3 derived from
+
sec. butyl chloride is more stable than the 1° carbonium ion CH3—CH2—CH2 derived from
n-propyl chloride. Therefore sec. butyl chloride gets hydrolyzed more easily than n-propyl
chloride under SN1 conditions.
Examination Papers 259
(iii) I
As Iodine is a better leaving group due to its larger size, it will be released at a faster rate in the
presence of incoming nucleophile.
26. a-Glucose and b-Glucose differ only in the configuration of hydroxy group at C1 and are called
anomers and the C1 carbon is called anomeric carbon. The six membered cyclic structure of glucose is
called pyranose structural (a-or b-), in analogy with pyrane. The cyclic structure of glucose is more
correctly represented by Haworth structure as given below.
6 CH2OH 6 CH2OH
5
O 5
O
O H H H H H OH
4 1 4 1
OH H OH H
HO 3
OH HO 3
H
2 2
Pyran
H OH H OH
a-D-(+) Glucopyranose b-D-(+) Glucopyranose
27.
Thermoplastics Thermosetting plastics
(i) These polymers are linear or slightly branched (i) These polymers are cross linked or heavily
chain molecules. branched molecules.
(ii) Soften on heating and harden on cooling and (ii) On heating undergo extensive cross linking in
can be remoulded. moulds and become infusible.
(iii) Some common examples are polyethene, (iii) Some common examples are bakelite,
PVC, polystyrene, etc. urea-formaldehyde resins, terylene, etc.
28. (a) (i) Mole fraction of a particular component in a solution may be defined as the ratio of
number of moles of that component to the sum of the moles of all the components present
in the solution. For a solution of two components A and B,
nA
Mole fraction of A, xA =
nA + nB
nB
Mole fraction of B, xB =
nA + nB
(ii) A solution which obeys Raoult’s law over the entire range of concentration and temperature,
and during the formation of which no change in enthalpy and volume takes place is called an
ideal solution. Thus for an ideal solution,
(i) Raoult’s law is obeyed, i.e., PA = PA° xA and PB = PB° xB
(ii) DHmix = 0
(iii) DVmix = 0
(b) WB = 15.0g; WA = 450g; D Kf = 1.86 K kg mol L–1
D Tf = 0°C – (– 0.34°C) = 0.34°C or 0.34 K
260 Xam idea Chemistry—XII
XeOF4
(b) (i) It is because S–S single bond is stronger than O–O single bond.
(ii) This is because the bond dissociation enthalpy of I–Cl bond is lower than that of I–I bond.
(iii) It is due to
l low enthalpy of dissociation of F–F bond
–
l high hydration enthalpy of F .
OR
(a) (i) 3Cu + 8HNO3 (dilute) ¾ ¾® 3Cu (NO3)2 + 2NO + 4H2O
(ii) XeF4 + O2F2 ¾ ¾® XeF6 + O2
(b) (i) It is because P–P single bond is stronger than N–N single bond.
(ii) Because of its small size, oxygen is capable of forming pp–pp bond and exist as diatomic
O2 molecule. The intermolecular forces in oxygen are weak van der Waals force, due to
which it is a gas at room temperature. On the other hand, sulphur, due to its larger size
prefers to form S–S single bond and exist as octaatomic S8 molecule having puckered ring
Examination Papers 261
structure. Because of larger size the force of attraction holding the S8 molecules together
are much stronger. Hence sulphur is a solid at room temperature.
(iii) All halogens are coloured. This is due to absorption of radiation in visible region which
results in the excitation of outer electrons to higher energy level while the remaining light
is transmitted. The colour of the halogen is the colour of transmitted light.
CrO3 - H2 SO4
30. (a) (i) CH3CH2CH2CH2.OH ¾ ¾ ¾ ¾¾¾ ¾® CH3CH2CH2COOH
Butan-ol Butanoic acid
–+
COCH3 COOK COOH
(ii) KMnO4/KOH dil. H2SO4
D – K2SO4
–+
CH3 COOK COOH
4-Methyl Benzene-1,4-
acetophenone dicarboxylic acid
(b) The compound is 2-ethyl benzaldehyde and the reactions involved in the question are given
below:
–
COO CH2OH
CH2CH3 CH2CH3
+
–
OH
–
COO CHO COOH
CH2CH3 +– CH2CH3 COOH
[Ag(NH3)2] OH (O)
Ag +
Tollens’ reagent
Silver 2-Ethyl 2-ethyl benzaldehyde Benzene-1,2-
mirror benzoate dicarboxylic acid
NO2
CH—NNH NO2
CH2CH3
+ H2O
2,4-DNP derivative
OR
(a) (i) Propanone on treatment with I2/NaOH (NaOI) undergoes iodoform reaction to give yellow
ppt of iodoform but propanol does not.
+
CH3COCH3 + 3NaOI ¾
¾® CH3COONa + CHI3¯ + 2NaOH
Propanone Iodoform
(ii) Benzaldehyde being an aldehyde reduces Tollens’ reagent to give silver mirror test but
acetophenone being a ketone does not give this test.
– Heat –
C6H5CHO + 2[Ag (NH3)2]+ + 3OH ¾ ¾¾® C6H5COO + 2H2O + 2Ag¯ + 4NH3
Benzaldehyde Tollen’s reagent Silver mirror
262 Xam idea Chemistry—XII
Hard water contains calcium and magnesium salts. In hard water, soap gets precipitated as calcium
and magnesium soap which being insoluble stick to the clothes as gummy mass. Therefore soaps do
not work in hard water.
20. At anode: Al ¾¾® Al3+ + 3e– ]×2
At Cathode: Ni2+ + 2e– ¾ ¾® Ni]×3
2+
Cell reaction: 2Al + 3Ni ¾ ¾® 2Al3+ + 3Ni
E oCell = E Cathode – E anode = E oNi 2+ / Ni – EAl
o o o
3+
/Al
0.059
= 1.41 V – (– 0.54)
6
E cell = 1.41 V + 0.0053 V
= 1.4153 V
23. (i) Interstitial compounds are well known for many of the transition elements because the
transition elements are capable of entrapping small sized atoms such as H,C and N in the
interstitial sites in their crystal lattices. These trapped atoms get bonded to the atoms of
transition elements, for example, TiC, Fe3H and Mn4N, etc.
(ii) The decrease in metallic radius coupled with increase in atomic mass results in a general
increase in density from titanium to copper in the first series of transition elements.
(iii) This is due to very small energy gaps between 5f, 6d and 7s subshells in actinoids.
27. (i) Elastomers: These are the polymers having the weakest intermolecular forces of attraction
between the polymer chains. The weak forces permit the polymer to be stretched. A few ‘cross
links’ are introduced between the chains, which help the polymer to retract to its original
position after the force is released as in vulcanised rubber. Elastomers thus possess an elastic
character, e.g., buna-S, buna-N, neoprene, etc.
(ii) Condenstaion Polymers: The condensation polymers are formed by the repeated condensation
reaction between different bifunctional or trifunctional monomer units usually with elimination
of small molecules such as water, alcohol hydrogen chloride, etc. Nylon 6, 6, Nylon 6, terylene
are some examples.
(iii) Addition polymers: Addition polymers are formed by repeated addition of same or different
monomer molecules. The monomers used are unsaturated compounds, e.g., alkenes, alkadienes
and their derivatives. Polythene is an example of addition polymer.
—CH2 ¾350–570
n CH2— ¾¾¾ K, 1000– 2000 atm
¾ ¾ ¾¾® –(CH2 — CH2 )– n
traces of O2
Ethene Polyethene
30. O
(a) (i) P
H OH
H
H3PO2
(b) (i) Nitrogen is much less reactive than phosphorus because of the high bond enthalpy of NºN
bond.
(ii) This is because in H2O hydrogen bond formed is three dimensional whereas in H–F it is
linear.
(iii) This is because S–S single bond is stronger than O–O single bond.
OR
H
O
O O O O O O
(a) (i) N N N N (ii) Cl
O O O O O
O
O
(N2O5)
Perchloric acid
(HClO4)
(b) (i) Due to smaller size of O as compared to S, the bond dissociation enthalpy of O–H bond is
higher than that of S–H bond. As a result, in aqueous solution, S–H bond can break more
easily form H+ ion than O–H bond. Hence H2S is more acidic than H2O.
(ii) This is because fluorine is the most electronegative element and it does not have d orbitals.
(iii) This is because the valence shell orbital of He is completely filled (1s2) and it has high
ionisation enthalpy and more positive electron gain enthalpy.
H OH
H
H3PO2
CH3
5. H2C—C—CH2—Br
3-Bromo-2-methyl propone
8. Human beings suffer from depression when they have low levels of noradrenaline. Noradrenaline is a
neurotransmiter that plays a role in mood changes. Low levels of noradrenaline lower the
signal-sending activity and make human beings suffer from depression. Tranquilizers such as
improniazid and phenelyzine are useful in treating this depression.
11. (i) In the extraction of silver, the metal is leached with dilute solution of NaCN. Dilute NaCN
solution forms a soluble complex with Ag while the impurities remain unaffected which are
then filtered off.
4Ag + 8NaCN + O2 + 2H2O ¾ ¾® 4Na[Ag(CN)2] + 4NaOH
Soluble complex
(ii) SiO2 acts as a flux in the extraction of copper. Sulphide ore of copper contains iron as impurity
which is removed as iron silicate (slag).
FeO + SiO2 ¾ ¾® FeSiO3
Flux Slag
Disinfectants
z Disinfectants are chemical substances which kill microorganisms or stop their growth but are
harmful to human tissues.
z Disinfectants are applied to inanimate objects such as floor, drainage system, instrument, etc.
z Chlorine in the concentration of 0.2 to 0.4 ppm in aqueous solution and SO in very low
2
concentration are disinfectants.
22. Three distinct features of chemisorptions which are not found in physisorptions:
(i) Enthalpy of adsorption: Enthalpy of adsorption is high (80-240 kJ mol–1) as it involves
chemical bond formation.
(ii) High specificity: Chemisorption is highly specific and it will only occur if there is some
possibility of chemical bonding between adsorbent and adsorbate. For example, hydrogen is
adsorbed by transition metals by virtue of hydride formation.
(iii) Irreversibility: Chemisorption is usually irreversible in nature as it involves compound
formation. It is very slow at low temperatures on account of high activation energy.
23. (i) Cr2+ is reducing agent as its configuration changes from d4 to d3, the later having a half-filled
trg level. On the other hand, the change from Mn2+ to Mn3+ results in the extra stable
half-filled, d5 configuration. Therefore Mn3+ is an oxidising agent.
(ii) This is due to small energy gap between 5f, 6d and 7s subshells in actinoids.
(iii) This is because with increase in atomic number in a series , the increased nuclear charge is
partly cancelled by the increased shielding effect of electrons in the d-orbitals of penultimate
shell.
266 Xam idea Chemistry—XII
H3C—CH—
—CH—CH—CH2—CH3
|
OH
6. Draw the molecular structure of the compound, 4-methylpent-3-en-2-one.
7. Write the full form of DNA and RNA.
8. What is meant by ‘narrow spectrum antibiotics’?
9. (a) Define any two of the following terms:
(i) van’t Hoff factor
(ii) Mole fraction
(iii) Ebullioscopic constant
(b) State Raoult’s law.
OR
The density of water of a lake is 1.25 g (mL) and one kg of this water contains 92 g of Na+ ions. what
–1
is the molarity of Na+ ions in the water of the lake? (Atomic mass of Na = 23.00 u)
10. Define the following terms:
(i) Order of a reaction
(ii) Activation energy of a reaction
268 Xam idea Chemistry—XII
11. Name one chief ore each of copper and aluminium. Name the method used for concentration of these
two ores.
12. Explain the following:
(i) The chemical reactivity of nitrogen is much less than that of phosphorus.
(ii) SF6 is kinetically inert.
13. Draw the molecular structures of the following species:
(i) H3PO3
(ii) BrF3
14. What are ambident nucleophiles? Explain giving an example.
15. Explain as to why
(i) Alkyl halides, though polar, are immiscible with water.
(ii) Grignard’s reagents should be prepared under anhydrous conditions.
16. Describe the following giving the chemical equation in each case:
(i) Carbylamine reaction
(ii) Hofmann’s bromamide reaction
17. Complete the following reaction equations:
(i) C6H5N2Cl + H3PO2 + H2O ¾ ¾®
(ii) C6H5NH2 + Br2(aq) ¾ ¾®
18. State a reason for each of the following statements:
(i) Soaps do not work in hard water.
(ii) The use of the sweetner aspartame is limited to cold foods and drinks.
19. Iron has a body centred cubic (bcc) unit cell with a cell dimension of 286.65 pm. The density of iron is
7.874 g cm–3. Use this information to calculate Avogadro’s number. (Atomic mass of Fe = 55.845 u)
OR
Silver crystallises in face centred cubic (fcc) unit cell. If the radius of silver atom is 145 pm, what is
the length of each side of the unit cell?
20. At 25°C the saturated vapour pressure of water is 3.165 kPa (23.75 mm Hg). Find the saturated
vapour pressure of a 5% aqueous solution of urea (carbamide) at the same temperature.
(Molar mass of urea = 60.05 g mol–1)
21. Consider the reaction:
2A + B ¾ ¾® C + D
Following results were obtained in experiments designed to study the rate of reaction:
Experiment Initial concentration (mol L–1) Initial rate
No. of formation
[A] [B]
HI
(iii) (CH3)3C—OC2H5 ¾¾ ®
26. What is glycogen? How is it different from starch? How is starch structurally different from
cellulose?
27. Write the structure of the monomer of each of the following polymers:
(i) Nylon-6
(ii) Teflon
(iii) Neoprene
28. (a) What type of a battery is the lead storage battery? Write the anode and the cathode reactions
and the overall reaction occurring in a lead storage battery sending out an electric current.
(b) A voltaic cell is set up at 25°C with the half-cells
Ag+ (0.001 M) | Ag and Cu2+ (0.10M) | Cu
What should be its cell potential? (E ocell = 0.46 V, log 105 = 5)
270 Xam idea Chemistry—XII
OR
(a) Define the term molar conductivity and explain how molar conductivity changes with solution
concentration for weak and strong electrolytes.
(b) A strip of nickel metal is placed in a 1-molar solution of Ni(NO3)2 and a strip of silver metal is
placed in a 1-molar solution of AgNO3. An electrochemical cell is created when the two
solutions are connected by a salt bridge and the two strips are connected by wires to a
voltmeter.
(i) Write the balanced equation for the overall reaction occurring in the cell and calculate the
cell potential
(ii) Calculate the cell potential, E, at 25°C for the cell if the initial concentration of Ni(NO3)2
is 0.100 molar and the initial concentration of AgNO3 is 1.00 molar.
[E oNi 2+ / Ni = – 0.25 V; EAg
o
2+
/Ag
= 0.80 V, log 10–1 = – 1]?
(b) How would you bring about the following conversions? Write the complete equation in each
case.
(i) Ethanol to 3-hydroxybutanal
(ii) Benzoic acid to m-nitrobenzyl alcohol
(iii) Benzaldehyde to benzophenone
Solutions
SET–I
1. The energy gap between valance band and conduction is known as forbidden zone.
2. As the adsorption progresses, the residual forces at the surface decreases resulting in the decrease of
surface energy which appears as heat.
¾® [Zn(CN) 4 ] 2- ( aq) + 2Ag( s)]
3. 2[Ag(CN) 2 ]( aq) + Zn( s) ¾
4. This is because hydrogen bonding is multidimensional in water whereas in HF it is linear.
5. Hex-4-en-3-ol
CH3 O
| |
6. — CH — C— CH3
CH3 —C —
7. DNA: Deoxyribonucleic acid
RNA: Ribonucleic acid
8. Antibiotics which are mainly effective against gram-positive or Gram-negative bacteria are known as
narrow spectrum antibiotics, e.g., ampicillin G.
9. (a) Van’t Hoff factor:
(i) May be defined as the ratio of normal molecular mass to observed molecular mass or the
ratio of observed colligative property to calculated colligative property.
(ii) Mole fraction may be defined as the ratio of number of moles of one component to the
sum of moles all the components present in a solution.
(iii) Ebuthoscopic constant may be defined as the elevation in boiling point when one mole of
a non-volatile solute is added to 1000 grams of solvent.
(b) It states that for a solution of volatile liquids the partial vapour pressure of each component in
the solution is directly proportional to its mole faction.
OR
92g
Number of moles of solute, Na+ ions = = 4 mol
23g mol -1
Mass of solution 1000 g 800 mL
Volume of solution = = - 1
= 800 mL = = 0.8 L
Density of solution 1. 25 g mL 1000 mL L-1
Number of moles Na + ions 4 mol
Molarity = =
Volume of solution in liter 0.8 L
= 5 mol L–1 or 5 m.
10. (i) The sum of the powers of the concentration of the reactants in the rate law expression is called
the order of the reaction. For a general reaction
aA + bB ¾ ¾® products
274 Xam idea Chemistry—XII
Let rate = K[ A ] m [ B ] n
Order of the reaction = m + n
(ii) The minimum extra energy absorbed by the reactant molecular so that their energy becomes
equal threshold energy is called activation energy.
Activation energy = Threshold energy – Energy possessed by reactant molecular
11.
Metal Chief ore Method of concentration
Copper Copper pyrite (CuFeS2) Froth floatation
Aluminium Bauxite [AlOx (OH)3–2x] Leaching
where 0 < x < 1
12. (i) As N N triple bond (941.4 kJmol–1) is much stronger than p–p single bond (213 kJmol–1),
therefore nitrogen is much less reactive than phosphorus.
(ii) This is because in SF6, sulphur is sterically protected by six fluorine atoms.
13. (i) H3PO3 (ii) BrF3—Slightly bent T
F
O
P Br F
H OH OH
F
14. Nucleophiles which can attack through the different nucleophilic centres present in it are called
ambident nucleophiles. For example, cyanide group is resonance hybrid of the following two
contributing structures:
C N C N
It can attack through carbon to form cyanide and through N to form isocyanide.
15. (i) This is due to inability of alkyl halides to form intermolecular hydrogen bonds with water
molecules.
(ii) This is because Grignard reagent forms alkanes by reacting with moisture.
RMgX + H2 O ¾ ¾® RH + Mg(OH)X
16. (i) Carbylamine reaction: Aliphatic and aromatic primary amines when heated with chloroform and
ethanolic potassium hydroxide form carbylamines or isocyanides which are foul smelling
substances. Secondary and tertiary amines do not show this reaction.
D
R—NH2 + CHCl3 + 3KOH (alc.) ¾¾ ® RNC + 3KCl + 3H2O
D
C6H5NH2 + CHCl3 + 3KOH (alc.) ¾¾ ® C6H5NC + 3KCl + 3H2O
Aniline Phenyl
isocyanide
(ii) Hoffmann’s bromamide reaction: When a primary acid amide is heated with bromine in an
aqueous or ethanolic solution of NaOH, a primary amine is obtained. The amine so obtained
contains one carbon less than that present in the amide.
Examination Papers 275
Br
Aniline 2,4,6-Tribromoaniline
18. (i) In hard water soaps get precipitated as calcium and magnesium soap which being insoluble in
water stick to the clothes as gummy mass.
(ii) This is because aspartame is unstable at cooking temperature.
19. Here, z = 2, M = 56 g mol–1, d = 7.87 g cm–3
a = 286.65 pm = 286 .65 × 10–10 cm = 2.8
Substituting the values in the expression,
z´ M
NA = 3 , we get
a ´d
2 ´ 56 g mol –1
NA =
( 286.65 ´ 10 -10 cm) 3 ´ 7.87 g cm –3
= 6.042 × 1023 mol–1
OR
For bcc unit cell, a = 2 2r
\ a = 2 2 × 145 pm
= 2 × 1.414 × 145 pm
a = 410.06 pm.
20. WB = 5 g, WA = 95 g, M B = 60.05 g mol–1,
MA = 18 g mol–1 P°A = 3.165 kPa
Substituting the values in the expression;
PAo - P WB ´ M A
= , we get
PAo M B ´ WA
-1
3.165 k Pa - P 5 g ´ 18 g mol
= = 0.015
3.165 k Pa 60.05 g mol -1 ´ 95g
P = 3.165 k Pa – 0.015 × 3.165 k Pa
P = 3.118 k Pa
276 Xam idea Chemistry—XII
(Xenon in excess)
24. (i) This is because the transition metals have empty d-orbitals into which the electron pairs can be
denoted by ligands containing and electrons, e.g., C6H6, C2H4 etc.
(ii) As only one inner d-orbital is available in nickel for bonding in the presence of strong ligand,
e.g., CO., CN.
Examination Papers 277
(iii) In both the complexes, Fe is in +2 oxide state with d6 configuration. As the ligands CN and
H2O possess different crystal field splitting energy (DO), they absorb different components of
visible light for d-d transition. Hence, the transmitted colours are different in dilute solutions.
25. (i) CH3—CH2—CH2—O—CH2—CH3—H—Br ¾
¾® CH3—CH2—Br—CH3—CH2—CH2—OH
OC2H5 OH
(iii) (CH3 ) 3 C — OC 2 H5 + HI ¾
¾® (CH3 ) 3 C — I + C 2 H5 — OH
26. Glycogen is a polymer of a - D -glucose. The carbohydrates are stored in animal body as glycogen.
Starch is also a polymer of a - D -glucose and consist of two components amylose and amylopectin.
Amylose is linear chain polymer of a - D –glucose. Both glycogen and amylopectin are branched
chain polymer of a - D - glucose but glycogen is more highly branched than amylopectin. Strarch is
the main storage polysaccharide of plants.
Starch is a polymer of a - D -glucose whereas cellulose is a polymer b–D–glucose.
27.
S.No. Polymer Monomer Structure of Monomer
(i) Nylon-6 Caprolactum H
H2C N C—O
H2C CH2
H2C CH2
Caprolactum
28. (a) Lead storage battery is a secondary battery. The reactions occurring in lead storage battery
when current is drawn from it are:
Anode: Pb(s) + SO42–(aq) ¾ ¾® PbSO4(s) + 2e–
Cathode: PbO2(s) + SO42–(aq) + 4H+(aq) + 2e– ¾ ¾®
PbSO4(s) + 2H2O(l)
Overall reaction: Pb(s) + PbO) 2+(s 2H2SO4(aq) ¾ ¾® 2PbSO 4(s) + 2H 2O(l)
(b) At Anode: Cu ¾ ¾® Cu2+ + 2e–
+ -
At Cathode: Ag + e ¾ ¾® Ag] ´ 2
o 0.059 ( 0.01)
\ E cell = 1.05V – log
2 (1) 2
Ecell = 1.05V – 0.0295 log 10–1 = 1.05 + 0.0295 V
Ecell = 1.0795 V
29. (a) (i) Cr2 O27- + 14H+ + 6e - ¾
¾® 2Cr 3+ + 7H2 O
2I– ¾® I2 + 2e–] × 3
¾
Cr2 O27- + 6I - + 14H+ ¾
¾® 2Cr 3+ + 3I 2 + 7H2 O
(ii) MnO-4 + 8H+ + 5e - ¾
¾® Mn 2+ + 4H2 O] ´ 2
SO23- + H2 O ¾® SO2-
¾ + -
4 + 2H + 2 e ] × 5
(ii) Cu2+ (aq) is much more stable than Cu(aq). This is because high negative enthalpy of
hydration of Cu2+(aq) easily compensates the high second ionisation enthalpy of copper.
Due to his Cu+(aq) undergo disproportionation as follows:
2Cu + ( aq) ¾
¾® Cu 2+ ( aq) + Cu( s)
(iii) This is due to high electronegativity oxygen and fluorine.
30. (a) Mechanism:
(i) Nucleophilic addition of Grignard reagent to carbonyl group to form an adduct.
+ – – +
d d d d – +
C O + R—Mg—X C—OMg—X
R
(ii) Hydrolysis of the adduct to alcohol.
– + H 2O
C—O—Mg—X C—O + Mg(OH)X
R R
(iii) P–Nitropropiophenone
NO2
OR
(a) (i) Cannizzaro reaction: Aldehydes which do not have an–a hydrogen atom, undergo
disproportionation reaction on treatment with concentrated alkali. In this reaction, one
molecule of the aldehyde is reduced to alcohol while another is oxidised to salt of
carboxylic acid.
–
2HCHO ¾conc.KOH
¾ ¾¾® CH3 OH + HCO O K +
Methyl alcohol Potassium formate
CH3
|
(b) (i) CH3 CHO ¾dil
¾NaOH
¾¾® CH3 — CH — CH2 — CHO
Ethanol 3 - Hydroxybutanol
CH2OH CH2—NH2
HNO2
NO2 NO2
p-Nitro benzyl alcohol
O
CHO COOH COCl
+ C
K2Cr2O7/H2SO4 SOCl2
(iii) (O) AlCl3 (anhyd.)
Benzaldehyde Benzoic Benzophenone
acid
SET–II
1. Metallic solid conducts electricity in solid state but ionic solid conducts electricity only in solution or
in molten state.
2. The catalytic reaction which depends upon the pore structure of the catalyst and the size of the
reaction and product molecules is called shape selective catalysis.
4. H2S, due to low bond dissociation enthalpy of H–S bond.
5. CH2 = CH - CH2 OH
8. (i) Thymine is present in DNA.
(ii) Uracil is present in RNA.
O O F
S S Xe
O O O O
OH HO F
282 Xam idea Chemistry—XII
22.
1. Particle Size Less than 1nm Between 1 nm to 1000 nm more than 1000 nm
2. Separation by
l ordinary filtration Not possible Not possible Possible
l ultra filtration Not possible Possible Possible
3. Settling of particles Do not settle Settle only on configuration Settle under gravity
OX OX
OX
Cr Cr
OX
OX
OX
dextro mirror laevo
Cl NH3 Cl NH3
Pt Pt
Cl NH3 H3N Cl
cis trans
Cl + Cl + Cl +
Cl Cl
en en
Co en Co Co en
en
Cl dextro en
trans cis mirror laevo
Geometrical isomers
Optical isomers
26. (i) Sucrose is dextrorotatory, on hydrolysis in the presence of hydrochloric acid or enzyme
invertase, it gives a mixture of D-(+)-glucose and D-(–)-fructose which is laeorotatory called
invert sugar.
(ii) If more than find-amino acids are joined together by peptide bend (CONH) the polyamide thus
formed is called polypeptide.
(iii) Enzymes are biocatalyst. Almost all the enzymes are globular proteins. Enzymes are specific in
nature and efficiency in their action. They are required in small quantity and highly active
optimum temperature range (298–310 K) and pH values 5–7.
SET–III
1. The substances which are weakly attracted by external magnetic field are called paramagnetic
substances and the property. Thus exhibited is called paramagnetism. Paramagnetism is shown by
those substances whose atoms, ions or molecules contain unpaired electron contain unpaired
electrons, e.g., O2, Cu2+ Fe3+, Cr3+, etc.
3. Depressant is used to prevent the formation of froth from one of the two sulphide ores.
4. Since the bond dissociation enthalpy of the H–Cl bond is lower than H–F bond therefore H–Cl is
stronger acid than H– F in aqueous solution.
5. 1-methoxy-2-methyl propane.
6. OH O
CH3—C—CH2—C—CH3
CH3
12. (i) This is because fluorine is most electronegative element and does not have d-orbitals in its
valence shell.
(ii) Due to vary high ionisation enthalpy helium does not form any real chemical compound.
14. (i) Dipole moment is a product of charge and distance. Since chlorobenzene has lower magnitude
of negative charge on Cl atom and shorter C—Cl bond than cyclohexyl chloride due to
resonance therefore chlorobenzene has lower dipole moment than cyclohexyl chloride.
284 Xam idea Chemistry—XII
(ii) This is because the new intermolecular attractions between haloalkenes and organic solvent
molecules have almost the same strength ones being broken in the separate haloalkan and
solvent molecules.
20. DTf = Tf0 - Tf = 0°C – (– 0.320°C) = 0.320°C = 0 or 0.320 K
m = 0.0711 mol kg–1, Kf = 1.86 K Kg mol–1, DTf = 0.320K
Substituting these values in the expression, DTf = iK f m, we get
. K kg mol–1 × 0.0711 mol kg–1
0.320 K = i´186
0.320
i= = 2.42
0.132
22. When the dispersion medium is water colloids are classified as hydrophilic colloids and hydrophobic
colloids. Hydrophilic colloids are solvent (water) attracting, reversible and quite stable, e.g., gum,
starch, gelatin etc. Hydrophobic colloids are solvent (water repelling, irreversible and less stable, e.g.,
metal sulphides sol, metal hydroxide sol, etc.
23. (i) Sn + 2PCl5 ¾heating
¾¾® SnCl4 + 2PCl3
(ii) 2Fe3+ + SO2 + 2H2O ¾¾® 2Fe2+ + SO2-
4 + 4H
+
SET–I
Time allowed : 3 hours Maximum marks: 70
General Instructions:
(i) All questions are compulsory.
(ii) Question numbers 1 to 8 are very short answer questions and carry 1 mark each.
(iii) Question numbers 9 to 18 are short answer questions and carry 2 marks each.
(iv) Question numbers 19 to 27 are also short answer questions and carry 3 marks each.
(v) Question numbers 28 to 30 are long answer questions and carry 5 marks each.
(vi) Use log tables, if necessary. Use of calculators is not allowed.
1. How many atoms constitute one unit cell of a face-centered cubic crystal?
2. Name the method used for the refining of nickel metal.
3. What is the covalency of nitrogen in N2O5?
4. Write the IUPAC name of CH3—CH—CH2—CH—CH2 .
|
Cl
5. What happens when CH3—Br is treated with KCN?
6. Write the structure of 3–methyl butanal.
7. Arrange the following in increasing order of their basic strength in aqueous solution:
CH3.NH2, (CH3)3N, (CH3)2NH
8. What are three types of RNA molecules which perform different functions?
9. 18 g of glucose, C6H12O6 (Molar Mass = 180 g mol–1) is dissolved in 1 kg of water in a sauce pan. At
what temperature will this solution boil?
(Kb for water = 0.52 K kg mol–1, boiling point of pure water = 373.15 K)
10. The conductivity of 0.20 M solution of KCl at 298 K is 0.025 S cm–1. Calculate its molar
conductivity.
11. Write the dispersed phase and dispersion medium of the following colloidal systems:
(i) Smoke (ii) Milk
OR
What are lyophilic and lyophobic colloids? Which of these sols can be easily coagulated on the
addition of small amounts of electrolytes?
286 Xam idea Chemistry—XII
12. Write the differences between physisorption and chemisorption with respect to the following:
(i) Specificity ( ii) Temperature dependence
(iii) Reversibility and (iv) Enthalpy change
13. (a) Which solution is used for the leaching of silver metal in the presence of air in the metallurgy of
silver?
(b) Out of C and CO, which is a better reducing agent at the lower temperature range in the blast
furnace to extract iron from the oxide ore?
14. What happens when
(i) PCl5 is heated? (ii) H3PO3 is heated?
Write the reactions involved.
15. (a) Which metal in the first transition series (3d series) exhibits +1 oxidation state most frequently
and why?
(b) Which of the following cations are coloured in aqueous solutions and why?
Sc3+, V3+, Ti4+, Mn2+
(At. nos. Sc = 21, V = 23, Ti = 22, Mn = 25)
16. Chlorobenzene is extremely less reactive towards a nucleophilic substitution reaction. Give two
reasons for the same.
17. Explain the mechanism of the following reaction:
+ · ·
H
2CH3—CH2—OH ¾ ¾¾® CH3CH2 — O —CH2—CH3 + H2O
413 K · ·
(c) What type of point defect is produced when AgCl is doped with CdCl2?
20. Determine the osmotic pressure of a solution prepared by dissolving 2.5 × 10–2 g of K2SO4 in 2 L of
water at 25oC, assuming that it is completely dissociated.
(R = 0.082 L atm K–1 mol–1, Molar mass of K2SO4 = 174 g mol–1).
21. Calculate the emf of the following cell at 298 K:
Fe (s) | Fe2+ (0.001 M) || H+ (1M) | H2 (g) (1 bar), Pt (s)
o
(Given E cell = + 0.44 V)
22. How would you account for the following?
(i) Transition metals exhibit variable oxidation states.
(ii) Zr (Z = 40) and Hf (Z = 72) have almost identical radii.
(iii) Transition metals and their compounds act as catalyst.
Examination Papers 287
OR
Complete the following chemical equations:
(i) Cr2 O72 – + 6Fe 2 + + 14H+ ¾ ¾
¾®
(ii) 2CrO24 – + 2H+ ¾ ¾
¾®
(iii) 2MnO–4 + 5C 2 O24 – + 16H+ ¾ ¾
¾®
23. Write the IUPAC names of the following coordination compounds:
(i) [Cr(NH3)3Cl3] (ii) K3[Fe (CN)6]
(iii) [CoBr2(en)2]+, (en = ethylenediamine)
24. Give the structures of A, B and C in the following reactions:
+
CuCN H O H NH 3
(i) C 6 H5 N+2 Cl – ¾ ¾ ¾¾® A ¾ ¾2¾ ¾¾® B ¾ ¾ ¾¾® C
D
+
Sn + HCl NaNO2 + HCl
H O H
(ii) C 6 H5 NO2 ¾ ¾ ¾ ¾¾® A ¾ ¾ ¾ ¾ ¾ ¾
¾® B ¾ ¾2¾ ¾¾® C
273 K D
25. Write the names and structures of the monomers of the following polymers:
(i) Buna–S (ii) Neoprene
(iii) Nylon–6, 6
26. After watching a programme on TV about the adverse effects of junk food and soft drinks on the
health of school children, Sonali, a student of Class XII, discussed the issue with the school principal.
Principal immediately instructed the canteen contractor to replace the fast food with the fibre and
vitamins rich food like sprouts, salad, fruits, etc. This decision was welcomed by the parents and the
students.
After reading the above passage, answer the following questions:
(a) What values are expressed by Sonali and the Principal of the school?
(b) Give two examples of water-soluble vitamins.
27. (a) Which one of the following is a food preservative?
Equanil, Morphine, Sodium benzoate
(b) Why is bithional added to soap?
(c) Which class of drugs is used in sleeping pills?
28. (a) A reaction is second order in A and first order in B.
(i) Write the differential rate equation.
(ii) How is the rate affected on increasing the concentration of A three times?
(iii) How is the rate affected when the concentrations of both A and B are doubled?
(b) A first order reaction takes 40 minutes for 30% decomposition. Calculate t1/2 for this reaction.
(Given log 1.428 = 0.1548)
OR
(a) For a first order reaction, show that time required for 99% completion is twice the time required
for the completion of 90% of reaction.
(b) Rate constant ‘k’ of a reaction varies with temperature ‘T’ according to the equation:
288 Xam idea Chemistry—XII
Ea æ 1 ö
log k = log A – ç ÷
2 . 303 R è T ø
1
Where Ea is the activation energy. When a graph is plotted for log k vs. , a straight line with a
T
slope of – 4250 K is obtained. Calculate ‘Ea’ for the reaction. (R = 8.314 JK–1 mol–1)
29. (a) Give reasons for the following:
(i) Bond enthalpy of F2 is lower than that of Cl2.
(ii) PH3 has lower boiling point than NH3.
(b) Draw the structures of the following molecules:
(i) BrF3 (ii) (HPO3)3
(iii) XeF4
OR
(a) Account for the following:
(i) Helium is used in diving apparatus.
(ii) Fluorine does not exhibit positive oxidation state.
(iii) Oxygen shows catenation behaviour less than sulphur.
(b) Draw the structures of the following molecules:
(i) XeF2 (ii) H2S2O8
30. (a) Although phenoxide ion has more number of resonating structures than carboxylate ion,
carboxylic acid is a stronger acid than phenol. Give two reasons.
(b) How will you bring about the following conversions?
(i) Propanone to propane
(ii) Benzoyl chloride to benzaldehyde
(iii) Ethanal to but-2-enal
OR
(a) Complete the following reactions:
conc. KOH
(i) 2H—C—H ¾ ¾ ¾¾¾ ¾®
||
O
Br2 P
(ii) CH3COOH ¾ ¾ ¾¾®
CHO
HNO3/H2SO4
(iii)
273–283 K
(b) Give simple chemical tests to distinguish between the following pairs of compounds:
(i) Ethanal and Propanal
(ii) Benzoic acid and Phenol
Examination Papers 289
SET–II
(Questions Uncommon to Set–I)
1. What type of stoichiometric defect is shown by AgCl?
CH3
|
2. Write the IUPAC name of CH3CH—CH — C —CH3.
|
Br
4. What type of bonding helps in stabilising the a-helix structure of proteins?
6. What inspired N. Bartlett for carrying out reaction between Xe and PtF6?
7. What happens when ethyl chloride is treated with aqueous KOH?
8. Write the structure of 4–chloropentan–2–one.
9. How will you convert the following?
(i) Propan–2–ol to propanone. (ii) Phenol to 2, 4, 6–tribromophenol
11. What is the difference between oil/water (O/W) type and water/oil (W/O) type emulsions? Give an
example of each type.
17. (a) Which of the following ores can be concentrated by froth floatation method and why?
Fe2O3, ZnS, Al2O3.
(b) What is the role of silica in the metallurgy of copper?
18. (a) Why does p-dichlorobenzene have a higher m.p. than its o- and m- isomers?
(b) Why is (±) – Butan-2-ol is optically inactive?
23. Write the names and structures of the monomers of the following polymers:
(i) Polystyrene (ii) Dacron
(ii) Teflon
27. Write the types of isomerism exhibited by the following complexes:
(i) [Co(NH3)5Cl]SO4 (ii) [Co(en)3]3+
(ii) [Co(NH3)6] [Cr(CN)6]
SET–III
(Questions Uncommon to Set-I and II)
1. What type of substances would make better permanent magnets, ferromagnetic or ferrimagnetic?
3. What is the composition of ‘Copper matte’?
5. What is a glycosidic linkage?
6. Write the IUPAC name of (CH3)2CH.CH (Cl)CH3.
7. Which compound in the following pair undergoes faster S N 1 reaction?
Cl Cl
and
290 Xam idea Chemistry—XII
27. Write the names and structures of the monomers of the following polymers:
(i) Bakelite (ii) Nylon-6
(iii) Polythene
zzz
Examination Papers 291
Solutions
SET–I
1 1
1. (8 corner atoms) ´ + (6 face centre atoms) ´ = 1 + 3 = 4
8 2
2. Mond Process.
3. 4
4. 4-Chloropent-1-ene.
5. CH3 Br + KCN ¾ ¾
¾® CH3 C ºº N
Ethanenitrile
4 3 2 1
6. CH3 ¾ CH¾ CH2 ¾ C HO
½
CH3
7. (CH3 ) 3 N < CH3 NH2 < (CH3 ) 2 NH
8. There are three types of RNAs:
(i) Ribosomal RNA (rRNA)
(ii) Messenger RNA (mRNA)
(iii) Transfer RNA (tRNA)
9. Moles of glucose = 18 g / 180 g mol -1 = 0.1 mol
Mass of solvent = 1 kg
Hence, molality of glucose solution = 0.1 mol kg–1
For water, change in boiling point will be
DTb = K b ´ m
= 0.52 K kg mol–1 × 0.1 mol kg–1 = 0.052 K.
Since water boils at 373.15 K at 1.013 bar pressure, the boiling point of solution will be 373.15 +
0.052 = 373.202 K.
-1 3 –1
10. L m = k ´ 1000 = 0.025 S cm ´ 1000 cm L = 125 S cm 2 mol - 1
c 0.20 mol L- 1
11.
Type of Colloid Dispersed Phase Dispersion Medium
(i) Smoke Solid Gas
(ii) Milk Liquid Liquid
OR
Lyophilic sols are solvents attracting sols whereas lyophobic sols are solvent repelling sols.
Lyophobic sols can be easily coagulated.
292 Xam idea Chemistry—XII
12.
Physisorption Chemisorption
(i) Specificity It is not specific in nature. It is highly specific in nature.
(ii) Temperature Low temperature is favourable for High temperature is favourable for
dependence adsorption. It decreases with increase of adsorption. It increases with the
temperature. increase of temperature.
(iii) Reversibility It is reversible in nature. It is irreversible.
(iv) Enthalpy change Enthalpy of adsorption is low Enthalpy of adsorption is high
(20–40 kJ mol -1) in this case. (80-240 kJ mol -1) in this case.
15. (a) Cu has the electronic configuration 3d 10 4s 1 . It can easily lose 4s 1 electron to give the stable
3d 10 configuration. Hence, it shows +1 oxidation state.
(b) Mn 2 + and V 3 + are coloured in aqueous solutions because they have unpaired electrons.
16. (i) Due to resonance C—Cl bond acquires a partial double bond character which is difficult to
cleave.
sp2 hybridisation of C of C—Cl bond.
(ii) Due to
(iii) Due to
unstable phenyl cation.
(iv) Due torepulsion between nucleophile and electron-rich arenes.
H
·· ½·
17. (i) CH3 ¾ CH2 ¾ O H + HÅ ¾® CH3CH2 ¾ O · ¾ H
·· Å
H
(ii) CH3—CH2—O + CH3—CH2—O CH3—CH2—O—CH2—CH3 + H2O
H
H H
+
(iii) CH3—CH2—O—CH2—CH3 CH3CH2—O—CH2—CH3 + H
H
18. (i) Propan-2-ol can be prepared from propene by hydration as shown below:
H O/ H+
— CH2 ¾ ¾2¾ ¾¾® CH3 — CH — CH3
CH3 — CH —
Propene ½
OH
Examination Papers 293
OH OH OH
H2SO4 (conc.) SO3H HNO3 (conc.) O2N NO2
(ii)
Phenol
SO3H NO2
Phenol-2,4 2,4,6-Trinitrophenol
disulphonic acid
19. (a) p-type semiconductor.
(b) Ferromagnetism.
(c) Impurity defect/cation vacancy defect.
20. K 2 SO4 dissolved = 0.025 g
Volume of solution = 2 L, T = 25°C = 298 K
Molar mass of K 2 SO4 = 174 g mol -1
Since K 2 SO4 dissociates completely as K 2 SO4 ¾® 2K + + SO24 -
Total number of moles of particle after dissociation 3
i= = =3
Number of moles of particles before dissociation 1
Applying van’t Hoff equation,
i ´ WB ´ R ´ T
p=
MB ´ V
3 ´ 0 . 025 g ´ 0.0821 L atm K -1 mol -1 ´ 298 K
= = 5.27 × 10–3 atm
174 g mol -1 ´ 2 L
21. Cell reaction: Fe(s) + 2H + (aq) ¾ ¾
¾® Fe 2 + (aq) + H 2 (g)
o 0.0591 [Fe 2 + ]
Nernst equation: E cell = E cell - log
2 [H+ ] 2
0.0591 10 - 3
\ E cell = 0.44 - log
2 (1) 2
0.0591
= 0.44 - ´ ( - 3) = 0.44 + 0.0886 = 0.52856V
2
22. (i) Transition elements show variable oxidation states because electrons in ns and ( n - 1) d-orbitals
are available for bond formation as they have nearly same energy.
(ii) This is due to filling of 4f orbitals which have poor shielding effect (lanthanoid contraction).
(iii) This is because of their ability to adopt multiple oxidation states and to form complexes.
OR
(i) Cr2O 27 – + 6Fe 2 + + 14H+ ¾ ¾
¾® 2Cr3+ + 6Fe3+ + 7H2O
26. (a) Values shown by Sonali: concern for the society, socially active and helpful to others.
Values shown by principal: caring, commanding and serious about the welfare of students.
(b) Vitamin B complex, Vitamin C.
27. (a) Sodium benzoate.
(b) Bithional acts as an antiseptic agent and reduces the odour produced by bacterial decomposition
of organic matter on the skin.
(c) Tranquilizers.
d[ R ]
28. (a) (i) Rate = - = k[ A ] 2 [ B ]
dt
(ii) When concentration of A is tripled
Rate = k [3A]2[B] = 9k [A]2[B]
i.e., Rate of reaction will become 9 times.
(ii) When concentration of both A and B is doubled
Rate = k [2A]2[2B] = 8k [A]2[B]
i.e., Rate of reaction will become 8 times.
(b) For a first order reaction
2.303 [R ]0
k= log
t [R ]
[R ]0 100 10
when t = 40 minutes, = =
[R ] 100 - 30 7
2.303 10 2.303
k= log = log 1.428
40 7 40
2.303
k= ´ 0.1548
40
Examination Papers 295
k = 8.91 ´ 10 - 3
min - 1
0.693 0.693
t1/2 = =
k 8.91 ´ 10 -3
t1/2 = 77.78 min.
OR
2. 303 [R ]0
(a) As t = log
k [R ]
2. 303 100
log
t 99% 1 = log 100 = 2
\ = k
t 90% 2. 303 100 log 10
log
k 10
Hence t 99% = 2t 90%
Ea
(b) Slope = - = - 4250 K
2. 303 ´ R
Ea = - 4250 × 2.303 × 8.314
= 81375 J mol–1
= 81.375 kJ mol–1
29. (a) (i) Bond dissociation enthalpy decreases as the bond distance increases from F2 to I2 because
of the corresponding increase in the size of the atom as we move from F to I. The F—F bond
dissociation enthalpy is, however, smaller than that of Cl—Cl and even smaller than that of
Br—Br. This is because F atom is very small and hence the three lone pairs of electrons on
each F atom repel the bond pair holding the F-atoms in F2 molecule. Hence, the bond
dissociation enthalpy increases in the order: I 2 < F2 < Br2 < Cl 2 .
(ii) Unlike NH3 , PH3 molecules are not associated through hydrogen bonding in liquid state.
That is why the boiling point of PH3 is lower than NH3 .
(b) (i) BrF3 (ii) (HPO3)3
F O
O O
P P OH
Br F HO
O O
P
F O OH
Slightly bent “T”
(iii) XeF4
F F
Xe
F F
Square planar
296 Xam idea Chemistry—XII
OR
(a) (i) Helium is used as a diluent for oxygen in modern diving apparatus because of its very low
solubility in blood.
(ii) This is because fluorine is the most electronegative element.
(iii) Because O—O single bond is weaker than S—S single bond.
(b) (i) Refer to Q. 12(ii) of CBSE (All India) Paper 2013.
(ii) H2S2O8
O O
S S
O O O O
OH OH
Peroxodisulphuric acid
(H2S2O8)
30. (a) (i) Resonating structures of carboxylate ion are more stable than phenoxide ion.
(ii) Negative charge is dispersing on two electronegative oxygens in carboxylate ion whereas it
is on one oxygen atom in phenoxide ion.
(b) (i) Propanone to Propane
O
||
Clemmensen reduction
CH3—C—CH3 ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾¾® CH3CH2CH3
Zn(Hg) + HCl
Propanone Or Propane
NH 2 — NH 2 + KOH + glycol
CHO CHO
HNO3/H2SO4
(iii)
273–283 K
NO2
(b) (i) Ethanal (CH3CHO) and propanal (CH3CH2CHO): Ethanal responds to iodoform test
and gives a yellow precipitate on addition of NaOH and I2, while propanal does not.
(ii) Phenol and benzoic acid: Benzoic acid reacts with NaHCO3 giving CO2 gas with
effervescence, whereas phenol does not Phenol decolourises Br2 water giving white
precipitate, whereas benzoic acid does not.
SET–II
(Questions Uncommon to Set–I)
1. Frenkel defect.
2. 4-Bromo-4-methylpent-2-ene.
4. The a-helix structure of proteins is stabilised by intramolecular H-bonding between C—O of one
amino acid residue and the N—H of the fourth amino acid residue in the chain.
6. Neil Bartlett observed that PtF6 reacts with O2 to yield an ionic solid, O+2 PtF6-
¾® O+2 [PtF6 ] -
O2 ( g) + PtF6 ( g) ¾ ¾
Here, O2 gets oxidised to O+2 by PtF6 .
Since the first ionisation enthalpy of Xe (1170 kJ mol -1 ) is fairly close to that of O2 molecule
(1175 kJ mol -1 ), Bartlett thought that PtF6 should also oxidise Xe to Xe + . This inspired Bartlett to
carry out the reaction between Xe and PtF6 . When Xe and PtF6 were mixed, a rapid reaction occurred
and a red solid with the formula, Xe + [ PtF6 ] – was obtained.
278 K
Xe + PtF6 ¾ ¾ ¾¾® Xe + [PtF6 ] -
Hydrolysis
7. CH3 CH2 Cl + KOH ( aq) ¾ ¾ ¾ ¾ ¾® CH3 CH2 — OH + KCl + H2 O
D Ethyl alcohol
Ethyl chloride
O
||
8. CH3—CH—CH2—C—CH3
|
Cl
OH O
| K 2 Cr2 O7 + H 2 SO4 ||
9. (i) CH3—CH—CH3 ¾ ¾ ¾ ¾ ¾ ¾ ¾¾® CH3—C—CH3
Propan-2-ol Propanone
OH OH OH
H2SO4 (conc.) SO3H HNO3 (conc.) O2N NO2
(ii)
Phenol
SO3H NO2
Phenol-2,4 2,4,6-trinitrophenol
disulphonic acid (Picric acid)
298 Xam idea Chemistry—XII
11. (i) Oil in water (o/w) type emulsions: In such emulsions oil is the dispersed phase and water is
the dispersion medium, e.g., milk, vanishing cream.
(ii) Water in oil (w/o) type emulsion: In such emulsions, water is the dispersed phase and oil is
the dispersion medium, e.g., butter, cod liver oil.
17. (a) ZnS. This is because the sulphide ore particles are preferentially wetted by oil and gangue
particles are preferentially wetted by water.
(b) Silica acts as a flux to remove iron oxide (FeO) as slag in the metallurgy of copper.
FeO + SiO2 ¾¾
¾® FeSiO3
Flux Slag
18. (a) It is due to symmetry of p-dichlorobenzene which fits in crystal lattice better than the o- and m-
isomers.
(b) (±)-Butan-2-ol exist in two eventiomeric forms which rotate the plane of polarised light in
opposite directions in equal amounts. Therefore, cancelling each other and becoming optically
inactive.
23.
Polymer Monomers and their structures
(i) Polystyrene CH—CH2
SET–III
(Questions Uncommon to Set-I and II)
1. Ferromagnetic.
3. Cu2S and FeS.
5. The linkage between two monosaccharide units through oxygen atom is called glycosidic linkage.
6. 2-Chloro-3-methylbutane.
7. Cl
Examination Papers 299
8. H3C CHO
9. Multimolecular colloids: In this type of colloids, colloidal particles are aggregates of large atoms or
molecules each having size in the colloidal range, e.g., sulphur sol, gold sol. Multimolecular colloids
are generally lyophobic in nature.
Macromolecular colloids: These are the solution containing macromolecules in the colloidal range,
e.g., starch, proteins, polyethene, etc. Macromolecular colloids are generally lyophilic in nature.
14. (a) Zone refining is used for production of semiconductors and other metals of very high purity like
germanium, silicon, boron, gallium and indium.
(b) Cryolite lowers the melting point of the mixture./Acts as an electrolyte./Acts as solvent for
alumina. (Any one)
17. (i) Refer to Q.23(iii) of CBSE Examination Paper (All India) 2013.
(ii) Because chloroform is slowly oxidised by air in the presence of light to an extremely poisonous
gas phosgene.
Light
2CHCl3 + O2 ¾ ¾ ¾¾® 2COCl2 + 2HCl
Chloroform Phosgene
zzz
CBSE Examination Papers
All India–2013
SET–I
Time allowed : 3 hours Maximum marks: 70
5. Rearrange the following compounds in the increasing order of their boiling points:
CH3—CHO, CH3—CH2—OH, CH3—CH2—CH3
6. Write the structure of n-methylethanamine.
7. What are the products of hydrolysis of sucrose?
8. Is –(CH2—CH )– n a homopolymer or a copolymer?
|
Cl
9. Account for the following:
(i) Schottky defects lower the density of related solids.
(ii) Conductivity of silicon increases on doping it with phosphorus.
10. Aluminium crystallises in an fcc structure. Atomic radius of the metal is 125 pm. What is the length of
the side of the unit cell of the metal?
11. The standard electrode potential (E°) for Daniell cell is + 1.1 V. Calculate the DG° for the reaction
Zn( s) + Cu 2 + ( aq) ¾ ¾
¾® Zn 2 + ( aq) + Cu( s)
(1 F = 96500 C mol–1).
12. (a) For a reaction A + B ® P, the rate law is given by,
r = k[ A ]1 / 2 [ B ] 2 .
What is the order of this reaction?
Examination Papers 301
(b) A first order reaction is found to have a rate constant k = 5.5 × 10–14 s–1. Find the half life of the
reaction.
13. (a) Name the method used for removing gangue from sulphide ores.
(b) How is wrought iron different from steel?
14. Draw the structures of the following molecules:
(i) XeOF4 (ii) H3PO3
15. How are interhalogen compounds formed? What general compositions can be assigned to them?
16. Explain the mechanism of the following reaction:
+
H
CH3—CH2—OH ¾ ¾¾® CH2—CH2 + H2O.
443 K
NH2
(iii) + HCl(aq)
(b) Which acid of each pair shown here would you expect to be stronger?
(i) F—CH2—COOH or Cl—CH2—COOH
OH
(ii) or CH3COOH
304 Xam idea Chemistry—XII
SET–II
(Questions Uncommon to Set–I)
1. Write the structure of 2-aminotoluene.
2. Which aerosol depletes ozone layer?
4. Ethanol is soluble in water. Why?
Br2 + NaOH
(iii) CH3—C—NH2 ¾ ¾ ¾ ¾ ¾¾® ?
||
O
27. Give reasons for the following:
(i) Oxygen is a gas but sulphur is a solid.
(ii) O3 acts as a powerful oxidising agent.
(iii) BiH3 is the strongest reducing agent amongst all the hydrides of Group 15 elements.
Examination Papers 305
SET–III
(Questions Uncommon to Set–I and II)
1. What is especially observed when a beam of light is passed through a colloidal solution?
2. What is the basicity of H3PO3 and why?
3. Write the IUPAC name of the following compound:
Cl
CH3
Cl
5. What are the products of hydrolysis of lactose?
6. Is (CH2—CH)n a homopolymer or a copolymer?
Solutions
SET–I
1. Chemisorption.
2. Electrolytic refining.
3. The poisonous gases which can be prepared from chlorine gas are phosgene gas (COCl2)/mustard gas
(ClCH 2 CH 2 SCH 2 CH 2 Cl)/chloropicrin or tear gas (CCl3NO2)/sulphur monochloride (S2Cl2) .
4. 2-Chloro-3,3-dimethylbutane or 3-Chloro-2,2-dimethylbutane.
5. CH3CH2CH3 < CH3CHO < CH3CH2OH.
6. CH3—NH—CH2CH3.
7. Sucrose on hydrolysis gives one molecule each of glucose and fructose.
8. Homopolymer.
9. (i) In Schottky defect as the number of ions are missing from their normal lattice sites, the mass
decreases whereas the volume remains the same. Due to this the density decreases.
(ii) This is due to availability of additional unpaired electrons on doping with phosphorous.
a
10. For an fcc unit cell, r =
2 2
a = 2 2r = 2 ´ 1. 414 ´ 125 = 353.5 pm.
11. D r G o = - nFE o (cell)
15. Interhalogen compounds are prepared by direct combustion or by the action of halogen on lower
interhalogen compounds. They can be assigned general composition as XX¢, XX¢3, XX¢5 and XX¢7
where X is halogen of larger size and X¢ of smaller size and X is more electropositive than X¢.
16. The mechanism of dehydration of ethanol involves the following steps:
Step 1: Formation of protonated alcohol:
H H H H H
½ ½ ·· Fast ½ ½ ½
+ ¾¾¾®
H — C —C — O — H + H ¬¾¾¾ H — C — C — O+ — H
· · ··
½ ½ ½ ½
H H H H
Ethanol Ethyl oxonium ion
Step 2: Formation of carbocation: It is the slowest step and hence, the rate determining step of the
reaction.
H H H H H
½ ½ ½+ Slow ½ ½ ··
H — C —C — O — H ¾¾¾®
¬¾¾¾ H — C — C + + H2 O
·· ··
½ ½ ½ ½
H H H H
Step 3: Formation of ethane by elimination of a proton
H H
½ ½ H H
H — C — C + ¬¾¾¾ ¾¾¾® C— —C + H+
½ ½ H H
Ethene
H H
The acid used in step 1 is released in step 3. To drive the equilibrium to the right, ethene is removed as
it is formed.
17. (i) Reimer-Tiemann reaction:
OH ONa ONa OH
CHCl2 CHO CHO
CHCl3 (aq.) NaOH NaOH H 3O +
340 K
Phenol Salicylaldehyde
(2-Hydroxybenzaldehyde)
18. Thermoplastic polymers: These polymers are capable of repeatedly softening on heating and
hardening on cooling. Example, polythene, polystyrene, etc.
Thermosetting polymers: These polymers on heating undergo extensive cross linking in moulds and
again become infusible. These cannot be reused. Example, bakelite, urea-formaldehyde resins, etc.
308 Xam idea Chemistry—XII
OR
Polymers which disintegrate by themselves over a period of time due to environmental degradation by
microorganisms are called biodegradable polymers. Example, PHBV (Poly-b-hydroxybutyrate-co-b-
hydroxyvalerate).
19. If rate at 293 K is R, rate at 313 K will be 4R.
k2 Ea éT2 – T1 ù
log = ê ú
k1 2 .303R ë T1 ´ T2 û
4R Ea é313 – 293 ù
log = ê 293 ´ 313 ú
R 2 .303R ´ 8. 314 ë û
E a é 20 ù
log 4 =
19.1471 êë 91709 úû
0 . 6021 ´ 19.1471 ´ 91709
Ea =
20
= 52863.2177 J mol–1 or 52.863 kJ mol–1
20. (i) Multimolecular colloids are aggregates of atoms or molecules each having size less than 1 nm
held together by van der Waals forces. Example, sulphur sol, gold sol.
(ii) Lyophobic sols are those sols in which the particles of the disperse phase have little affinity for
the particles of the dispersion medium. Example, sols of metal and their sulphides and
hydroxides, As2S3 sol, Fe(OH)3 sol.
(iii) Emulsion is a colloidal solution in which both the dispersed phase and dispersion medium are
liquids. Example, milk, cod liver oil, etc.
21. (i) N due to the absence of d-orbitals, cannot form pp - dp multiple bonds. Thus, N cannot expand
its covalency beyond four but in R3N—O, N has a covalency of 5. So, the compound
R3N—O does not exist. On the other hand, P due to the presence of d-orbitals forms
pp - dp multiple bonds and hence can expand its covalency beyond 4. Therefore, P forms
R3P—O in which the covalency of P is 5.
(ii) Because Pb is in +4 oxidation state in PbCl4 and has high charge/size ratio than Pb2+, thus
polarising power of Pb4+ is greater than Pb2+, and hence it is more covalent.
(iii) N2 is less reactive at room temperature because of strong pp - pp overlap resulting into the
triple bond (N ºº N), consequently high bond dissociation enthalpy.
22. (i) Tetrachloridonickelate(II) ion.
(ii) sp3 hybridisation.
(iii) Tetrahedral.
OR
The difference of energy between two sets of degenerate orbitals as a result of crystal field splitting is
known as crystal field splitting energy.
(i) t 24g e g0
(ii) t 23g e1g
Examination Papers 309
23. (i) Since I - ion is a better leaving group than Br - ion, hence, CH3 I reacts faster than CH3 Br in
SN2 reaction with OH– ion.
(ii) (±) 2-Butanol is a racemic mixture, i.e., there are two enantiomers in equal proportions. The
rotation by one enantiomer will be cancelled by the rotation due to the other isomer, making the
mixture optically inactive.
(iii) In CH3–X the carbon atom is sp2 hybridised while in halobenzene the carbon atom is sp3
hybridised. The sp2 hybridised carbon is more electronegative due to greater s-character and
holds the electron pair of C–X bond more tightly than sp3 hybridised carbon with less
s-character. Thus, C–X bond length in CH3–X is bigger than C–X in halobenzene.
24. (i) CH3CH2NH2 + CHCl3 + 3KOH(alc.) ¾ ¾
¾® CH3CH2NC + 3KCl + 3H2O
H O
(ii) C6H5N+2 Cl – ¾ ¾ ¾ ¾2¾ ¾ ¾® C6H5OH + N2 + HCl
Room temperature
–
NH2 NH3Cl
(iii) + HCl(aq)
[10 –6 ]
= 0.46 – 0.02955 log
[ 0 .1]
= 0.46 + 0.0295 ´ 5
= 0.6075 V.
27. (i) Helpfulness, caring, generosity, kindness attitude towards poor.
(ii) Vitamin B12.
(iii) Vitamin C.
28. (a) For a solution of volatile liquids, Raoult’s law states that the partial vapour pressure of each
component of the solution is directly proportional to its mole fraction present in solution, i.e.,
p A µ x A , or p A = p Ao x A
According to Henry’s law, the partial pressure of a gas in vapour phase (p) is directly
proportional to mole fraction (x) of the gas in the solution.
p = KHx
On comparing it with Raoult’s law it can be seen that partial pressure of the volalite component
or gas is directly proportional to its mole fraction in solution.
p µx
only the proportionality constant KH differs from p Ao . Thus, it becomes a special case of Henry's
law in which KH = p Ao .
K f ´ WB ´ 1000
(b) Substituting the values of various terms involved in equation M B = , we get
DTf ´ WA
5.12 K kg mol -1 ´ 1. 00 g ´ 1000 g kg -1
MB = = 256 g mol -1
0. 40 K ´ 50 g
OR
(a) (i) Ideal solution: The solution which follows Raoult’s law at all concentrations and temperatures.
(ii) Azeotrope: A liquid mixture which distills at constant temperature without undergoing
any change in composition.
(iii) Osmotic pressure: The minimum excess pressure that has to be applied on the solution
side when the solution and solvent are separated by a semipermeable membrane to stop
osmosis.
(b) 10% w/w solution of glucose means 10 grams of glucose is present in 100 g of solution, i.e., 90 g
of water.
1000 ´ wt% 1000 ´ 10
m= = = 0.617 m
(100 - wt%) ´ Molecular weight of solute (100 - 10) ´ 180
29. (a) (i) Mn 3 + (3d4) is a good electron acceptor as the resulting species is more stable (3d5).
(ii) The E° (M 2 + / M) values are not regular which can be explained from the irregular
variation of ionisation enthalpies ( Di H1 + Di H 2 ) and also the sublimation enthalpies
which are relatively much less for manganese and vanadium.
(iii) Due to multiple bond formation ability of oxygen with Mn in Mn2O7.
Examination Papers 311
(b) (i) Pentan-2-one and pentan-3-one: Pentan-2-one responds to iodoform test and gives yellow
coloured precipitate with I2 and NaOH, while pentan-3-one does not.
(ii) Ethanal and propanal: Ethanal responds to iodoform test and gives yellow coloured
precipitate with I2 and NaOH, while propanal does not.
OR
Zn – Hg
(a) (i) CH3—C—CH3 ¾ ¾ ¾¾ ¾® CH3—CH2—CH3 + H2O
|| conc. HCl
O
Pd – BaSO4
(ii) CH3—C—Cl + H2 ¾ ¾ ¾¾¾ ¾® CH3—CHO + HCl
||
O
COOH COOH
Br2/FeBr3
(iii) + HBr
Br
(b) (i) F—CH2—COOH > Cl—CH2—COOH, because of higher –ve I effect of F.
OH
SET–II
CH3
1.
NH2
2. CCl2F2/Freon.
4. Alcohols can form H-bonds with water and break the H-bonds already existing between water
molecules. Hence, they are soluble in water.
5. 2-Bromo-4-chloropentane.
7. Peptide linkage.
8. Nylon-6,6/Dacron/Glyptal.
9. (a) Excess of lithium leads to metal excess defect. Lithium atoms lose electrons to form Li+ ions.
These electrons diffuse into the crystal and form F-centres. Therefore, LiCl crystals become pink.
(b) Number of P atoms per unit cell = 1 (at the body centre) ´ 1 = 1
1
Number of Q atoms per unit cell = 8 (at the corners) ´ = 1
8
Hence, the formula of the compound = PQ.
14. (i) XeF6 (ii) H2S2O7
F O O
F
F
Xe S S
F O O O
F OH OH
F
18. (i) Zone refining: Zone refining is based on the principle that the impurities are more soluble in
the melt than in the solid state of metal.
(ii) Vapour phase refining: In this, metal is converted into its volatile compound and collected
elsewhere. It is then decomposed to give pure metal.
19. (i) Associated colloids: There are certain substances which at low concentrations behave as
normal strong electrolytes, but at higher concentrations exhibit colloidal behaviour due to the
formation of aggregates. Such colloids are known as associated colloids or micelles, e.g., soaps
and detergents.
(ii) Lyophilic sol: Lyophilic sols are those sols in which the particles of dispersed phase have great
affinity for the dispersion medium, e.g., sols of gum, gelatin, starch, etc.
(iii) Adsorption: The accumulation of molecular species at the surface rather than in the bulk of a
solid or liquid is termed adsorption, e.g., water vapours on silica gel, poisonous gases on
charcoal.
H PO + H O
22. (i) C6H5N+2 Cl– ¾ ¾3¾ 2¾ ¾2¾
¾® C6H6 + N2 + H3PO3 + HCl
Examination Papers 313
NH2 NH2
Br2(aq) Br Br
(ii)
Br
Br + 4NaOH
(iii) CH3—C—NH2 ¾ ¾ 2¾ ¾ ¾¾® CH3—NH2 + Na2CO3 + 2NaBr + 2H2O
||
O
27. (i) Oxygen forms pp - pp multiple bonds. Due to small size and high electronegativity oxygen
exists as diatomic (O2 ) molecules. Whereas, sulphur because of its bigger size and lower
electronegativity, has a much greater tendency for catenation than oxygen and lower tendency
for pp - pp multiple bonds.
(ii) Due to the ease with which it liberates atoms of nascent oxygen, it acts as a powerful oxidising
agent.
(iii) This is because Bi—H bond is the weakest among the hydrides of group 15.
SET–III
1. Tyndall effect/Illumination of the path of light.
2. As two P—OH bonds are present in the molecule, therefore, its basicity is two.
3. 2, 5-Dichlorotoluene/1,4-Dichloro-2-methylbenzene.
5. Glucose and galactose.
6. Homopolymer.
8. H2C—HC—CH2
|
NH2
O O Xe
O
N N
O O F
Linear
(ii) Peptisation: The process of conversion of a freshly prepared precipitate into a colloidal
solution by shaking it with dispersion medium in the presence of a suitable electrolyte is called
peptisation. Example, freshly prepared precipitate of Fe(OH)3 is peptised by FeCl3.
(iii) Emulsion: These are the colloidal systems in which both the dispersion medium and the
dispersion phase are liquid, e.g., milk is an emulsion of fat in water.
21. (i) Nitrogen does not have d-orbitals in its valence shell to expand its covalence beyond four. That
is why it does not form pentahalide.
(ii) Lower value of bond dissociation enthalpy of F2 is due to the strong repulsion between the
non-bonding electrons of F atoms in the small sized F2 molecule.
(iii) Because of resonance.
27. 2 HNO
(i) CH3 CH2 NH2 ¾ ¾ ¾¾ ® CH3 CH2 OH
0°C
O O
(ii) S—Cl + H—N—C2H5 S—N—C2H5 + HCl
O H O H
O
O
N—H CH3—C—Cl
N—C—CH3
(iii) H Base H
zzz
CBSE Examination Papers
Foreign–2013
SET–I
Time allowed: 3 hours Maximum marks: 70
OR
(a) What are the constituents of ‘copper matte’?
(b) What is the role of depressant in froth floatation process?
15. Arrange the following in the order of property indicated for each set:
(a) HF, HCl, HBr, Hl — increasing acid strength.
(b) NH3, PH3, AsH3, SbH3, BiH3 — increasing reducing power.
16. Write the reactions involved when D-glucose is treated with the following reagents:
(a) HCN (b) Br2-water
17. (a) What type of bonding helps in stabilising the a-helix structure of proteins?
(b) What is the structural difference between a nucleoside and a nucleotide?
18. Arrange the following polymers in increasing order of their intermolecular forces:
(a) Nylon-6,6, Buna-S, Polythene
(b) PVC, Nylon-6, Neoprene
19. An element with molar mass 27 g mol–1 forms a cubic unit cell with edge length 4.05 × 10–8 cm. If its
density is 2.7 g cm–3, what is the nature of the cubic unit cell?
20. For a chemical reaction R ® P, the variation in the concentration ln [R] vs. time t plot is given as
In [R]
t(s)
For this reaction
(i) what is the order of the reaction?
(ii) what is the slope of the curve?
(iii) what is the unit of rate constant ‘k’?
21. Draw the structures of the following molecules:
(i) N2O5 (ii) H3PO2
(iii) XeF6
22. Account for the following:
(i) White phosphorus is more reactive than red phosphorus.
(ii) SnCl4 is more covalent than SnCl2.
(iii) O3 is a powerful oxidising agent.
OR
Complete the following equations:
(i) PC13 + H2O ¾ ¾
¾® (ii) XeF2 + PF5 ¾ ¾
¾®
heat
(iii) NaN3 ¾ ¾ ¾¾®
Examination Papers 317
Y X Y
CH3 Y CH3 CH3
(B) (A) + (B) (A)
This can result in giving compound (A) or (B) or both. What is the process called if
(i) (A) is the only compound obtained?
(ii) (B) is the only compound obtained?
(iii) (A) and (B) are formed in equal proportions?
25. (a) Explain the mechanism of the following reaction:
+
H
2CH3CH2OH ¾ ¾¾® CH3CH2—O—CH2CH3 + H2O
413 K
(b) Name the reagent used in the oxidation of ethanol to ethanoic acid.
26. How will you convert the following:
(i) Aniline to chlorobenzene
(ii) Ethanoic acid to methanamine
(iii) Benzene diazonium chloride to phenol
27. Mr. Naresh works in a multi-national company. He is stressed due to his hectic schedule. Mr. Amit,
his friend, comes to know that he has started taking sleeping pills without consulting the doctor.
Mr. Amit requests Naresh to stop this practice and takes him to a Yoga centre. With regular Yoga
sessions, Mr. Naresh is now a happy and relaxed man.
After reading the above passage, answer the following questions:
(i) Write the values shown by Mr. Amit.
(ii) Which class of drugs is used in sleeping pills?
(iii) Why is it not advisable to take sleeping pills without consultation with the doctor?
28. (a) State Kohlrausch’s law of independent migration of ions. Mention one application of
Kohlrausch’s law.
(b) The resistance of a conductivity cell containing 10–3 M KCl solution at 25ºC is 1500 W. What is
the cell constant if conductivity of 10–3 M KCl solution at 25°C is 1.5 × 10–4 S cm–1?
OR
Calculate emf and DG º for the following cell at 298 K:
Mg(s) | Mg2+(10–3 M) | | Cu2+(10–4 M) | Cu(s)
Given E o = – 2.36 V and E o = + 0.34 V
Mg 2+ Mg Cu 2+ Cu
(1 F = 96500 C mol–1)
318 Xam idea Chemistry—XII
SET–II
Questions Uncommon to Set-I
1. Why is glass considered a supercooled liquid?
2. Ethylamine is soluble in water whereas aniline is almost insoluble. Why?
4. Write the structure of 4-methyl pent-3-en-2-one.
Examination Papers 319
SET–III
Questions Uncommon to Set-I and II
1. What is the two-dimensional coordination number of a molecule in a square close-packed layer?
2. Write the IUPAC name of the following compound:
Cl
NO2
NO2
3. Write the names of monomers of the following polymer:
—[ C— (CH2 ) 5 — N]-n
|| |
O H
4. Why are diazonium salts of aromatic amines more stable than those of aliphatic amines?
320 Xam idea Chemistry—XII
zzz
Examination Papers 321
Solutions
1. Metallic solids.
2. Osmotic pressure.
3. Zone refining method.
4. 2-Chloro-3-methylbutane.
5. phenol < 4-nitrophenol < 2,4,6-trinitrophenol
OH O
½ ½½
6. H3 C ¾ C H ¾ CH2 ¾ C ¾ H
7. Methylamine is more basic than aniline due to resonance in aniline and lower stability of aniline ions.
8. Hexamethylenediamine [H2 N — (CH2 ) 6 — NH2 ] and adipic acid [HOOC — (CH2 ) 4 — COOH] .
9. Here, k H = 4.27 ´ 105 mm Hg
p = 760 mm Hg
According to Henry’s law, p = k H x CH 4
p 760 mm Hg
\ x CH 4 = = = 1.78 ´ 10 -3
kH 5
4. 27 ´ 10 mm Hg
Mole fraction of methane in benzene; x CH 4 = 1.78 × 10–3. 2
10. (i) The bonds between chloroform molecules and molecules of acetone are dipole–dipole
interactions but on mixing, the chloroform and acetone molecules, they start forming hydrogen
bonds which are stronger bonds resulting in the release of energy. This gives rise to an increase
in temperature.
(ii) When a non-volatile solute is dissolved in a solvent, the vapour pressure decreases. As a result,
the solvent freezes at a lower temperature.
2.303 [R ]0 [R ]0
11. t = log as [ R ] =
k [R ] 10
2. 303 [R ]0 2. 303 2. 303
\ t = log = ´ log 10 = ´ 1 = 3.838 ´ 10 - 2 s
k [R ]0 60 60
10
12. (a) It is converted into colloidal state.
Fe(OH)3 + FeCl3 ¾ ¾ ¾® [Fe(OH)3Fe]3+ + 3Cl–
(b) Powdered substances have greater surface area as compared to their crystalline forms. Greater
the surface area, greater is the adsorption.
13. (i) Lyophobic sols: Particles of dispersed phase have no affinity for dispersion medium, rather
they hate dispersion medium. They are not easily prepared and need stabilizing agents for their
preservation. They are irreversible. Examples: sols of gold, silver, Fe(OH) 3 , As 2 O3 etc. They
are also called extrinsic colloids.
322 Xam idea Chemistry—XII
(ii) Lyophilic sols: Particles of dispersed phase have great affinity for the dispersion medium.
They are self-stabilized because of strong attractive forces operating between the suspended
particles and the dispersion medium. They are reversible in nature. Examples: gums, gelatin,
starch, albumin, etc. They are also known as intrinsic colloids.
14. Leaching of aluminium from bauxite: Finely powdered bauxite ore is digested with an aqueous
solution of sodium hydroxide at 473–523 K and 35–36 bar pressure. Al2O3 is leached out as sodium
aluminate (and SiO2 too as sodium silicate) leaving impurities behind.
Al 2 O3 ( s) + 2NaOH( aq) + 3H2 O ¾ ¾
¾® 2Na[Al(OH) 4 ]( aq)
The aluminate in solution is neutralised by passing CO2 gas and hydrated Al2O3 is precipitated. At
this stage, the solution is seeded with freshly prepared samples of hydrated Al2O3 which induces the
precipitation.
2Na [Al(OH) 4 ]( aq) + CO2 ( g) ¾ ¾
¾® Al 2 O3 . xH2 O + 2NaHCO3 ( aq)
The sodium silicate remains in the solution and hydrated alumina is filtered, dried and heated to get
back pure Al2O3.
1470 K
Al 2 O3 . xH2 O( s) ¾ ¾ ¾ ¾® Al 2 O3 ( s) + xH2 O( g)
OR
(a) Cu2S and FeS.
(b) In froth floatation process, the role of the depressant is to prevent certain type of particles from
forming the froth with the air bubbles.
15. (a) HF < HCl < HBr < HI.
(b) NH3 < PH3 < AsH3 < SbH3 < BiH3.
16. (a) HCN
CHO CN
CH
| | OH
HCN
(CHOH) 4 ¾ ¾ ¾¾® (CHOH) 4
| |
CH2 OH CH2 OH
D-Glucose Glucose cyanohydrin
(b) Br2-water
CHO COOH
| |
Br water
(CHOH) 4 ¾ ¾ 2¾ ¾¾® (CHOH) 4
| |
CH2 OH CH2 OH
D-Glucose Gluconic acid
17. (a) Hydrogen bonds (intermolecular) between the C—O of one amino acid residue and N—H of the
fourth amino acid residue in the chain give stability to the structure.
(b) A nucleoside is formed of pyrimidine or purine base connected to C-1 of sugar (ribose or
deoxyribose) by a b-linkage.
Examination Papers 323
19. Density, d = Z ´ M d ´ a3 ´ NA
or Z = ...(i)
a3 ´ NA M
Here, M = 27 g mol -1
a = 4.05 ´ 10 -8 cm
d = 2.7 g cm -3
NA = 6.022 ´ 10 23 mol -1
Substituting these values in expression (i), we get
2.7 g cm -3 ´ ( 4.05 ´ 10 -8 cm) 3 ´ 6.022 ´ 10 23 mol -1
Z =
27 g mol -1
Z = 3.99 = 4
Thus, there are 4 atoms of the element present per unit cell. Hence, the cubic unit cell must be
face-centred.
20. For this reaction
(i) First order
(ii) – k (rate constant)
(iii) time–1 (s–1)
21. (i) N2O5 (ii) H3PO2 (iii) XeF6
O F
O O O
N N F F
P
O O Xe
H OH
F F
H
F
324 Xam idea Chemistry—XII
22. (i) This is due to polymeric structure of red phosphorus or angular strain in P4 molecule of white
phosphorus where the angle is only 60°.
(ii) The oxidation states of central atom Sn in SnCl4 and SnCl2 are +4 and +2 respectively. +4 state
of Sn has higher polarising power which, inturn, increase the covalent character of bond
formed between the central atom and the other atoms.
(iii) Due to the ease with which it liberates atoms of nascent oxygen, it acts as a powerful oxidising
agent.
O3 ¾® O2 + O (nascent oxygen)
¾¾
OR
(i) PCl3 + 3H2O ¾ ¾
¾® H3PO3 + 3HCl
¾® [XeF] + [PF6 ] -
(ii) XeF2 + PF5 ¾ ¾
heat
(iii) 2NaN3 ¾ ¾ ¾¾® 2Na + 3N2
23. (a) Dibromobis (ethane-1, 2-diamine) cobalt
(b) Ionisation isomerism.
(c) Because in case of CO back bonding takes place in which the central metal uses its filled d orbital
with empty anti-bonding p* molecular orbital of CO.
24. (i) Retention
(ii) Inversion
(iii) Racemisation
H
Å
·· ½·
25. (a) CH3 ¾ CH2 ¾ O H + H ¾® CH3 — CH2 ¾ O ·¾ H
·· Å
H
CH3—CH2—O + CH3—CH2—O CH3—CH2—O—CH2—CH3 + H2O
H
H H
+
CH3—CH2—O—CH2—CH3 CH3—CH2—O—CH2—CH3 + H
H
(b) Tollens’ reagent.
= [ lo + lo ] + [ lo + l Cl – ] - [ lo + lo ]
CH 3 COO- Na + H+ Na + Cl –
1
(b) Conductivity (k) = × Cell constant
Resistance ( R)
k = 1.5 ´ 10 -4 S cm -1 , R = 1500 ohm
1
1.5 ´ 10 -4 = ´ Cell constant
1500
\ Cell constant = 1.5 ´ 10 -4 ´ 1500 = 0.225 cm -1
326 Xam idea Chemistry—XII
OR
Cell reaction: Mg + Cu 2 + ¾ ¾
¾® Mg 2 + + Cu; n = 2
o 0.0591 [Mg 2 + ]
Nernst equation: E cell = E cell - log
2 [Cu 2 + ]
0.0591 10 - 3
\ E cell = 0.34 - ( - 2.36) - log
2 10 - 4
= 2.70 – 0.02655 = 2.67 V
o
DG ° = – nFE cell
DG ° = – 2 × 96500 × 2.71
= – 5.23 × 105 J mol–1
= – 5.23 × 102 kJ mol–1
29. (i) In the formation of metallic bonds, no electrons from 3d-orbitals are involved in case of zinc,
while in all other metals of the 3d series, electrons from the d-orbitals are always involved in
the formation of metallic bonds. That is why, the enthalpy of atomisation of zinc is the lowest
in the series.
(ii) This is due to filling of 4f orbitals which have poor shielding effect (lanthanoid contraction).
(iii) Transition elements show variable oxidation states because electrons in ns and ( n - 1) d-orbitals
are available for bond formation as they have nearly same energy.
(iv) This is because the sum of enthalpies of sublimation and ionisation is not balanced by
hydration enthalpy.
(v) Cr2+ is a stronger reducing agent because after the loss of one electron Cr2+ becomes Cr3+
which has more stable t 23g (half-filled) configuration in a medium like water.
OR
It is prepared by fusion of pyrolusite, MnO2, with KOH in the presence of an oxidising agent like
KNO3. This produces the dark green potassium manganate, K2MnO4 which disproportionates in a
neutral or acidic solution to give purple permanganate.
2MnO2 + 4KOH + O2 ¾ ¾
¾® K2MnO4 + 2H2O
3MnO42– + 4H+ ¾ ¾ ¾® 2MnO4– + MnO2 + 2H2O
Commercially, it is prepared by alkaline oxidative fusion of MnO2 followed by the electrolytic
oxidation of manganate (VI).
Fused with KOH
MnO2 ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾¾® MnO24 –
oxidised with air or KNO3 Manganate ion
Electrolytic oxidation
MnO24 – ¾¾¾¾¾¾¾¾
¾® MnO–4
in alkaline solution Permanganate
In the laboratory, KMnO4 is prepared by oxidation of manganese (II) ion salt by peroxodisulphate.
2Mn2+ + 5S2O82– + 8H2O ¾ ¾
¾® 2MnO4– + 10SO42– + 16H+
Peroxodisulphate Permanganate
Examination Papers 327
30. (a) (i) This is due to steric and electronic reasons. Sterically, the presence of two relatively large
substituents in ketones hinders the approach of nucleophile to carbonyl carbon than in
aldehydes having only one such substituent. Electronically two alkyl groups reduce the
positivity of the carbonyl carbon more effectively in ketones than in aldehydes.
(ii) This is because for aldol condensation to take place, at least one a-hydrogen (i.e., hydrogen
at carbon adjacent to carbonyl carbon) should be available, which is not present in
(CH3)3C—CHO.
(iii) This is due to more extensive association of carboxylic acid molecules through intermolecular
hydrogen bonding. The hydrogen bonds do not break completely even in the vapour phase.
(b) (i) Acetophenone and benzophenone:
Acetophenone responds to iodoform test and gives a yellow precipitate on addition of
NaOH and I2, but benzophenone does not.
COCH3 I2 /NaOH
COONa
+ 3NaOI + CHI3 ¯ + 2NaOH
Heat
Yellow ppt.
Sodium (Iodoform)
Benzoate
(ii) Benzaldehyde and Ethanal
Ethanal reacts with NaOI (I2/NaOH) to form yellow precipitate of iodoform while
benzaldehyde does not give this test.
– +
CH3CHO + 3I2 + 3NaOH ¾ ¾
¾® HCOO Na + CHI3 ¯ + 3NaI + 3H2O
Iodoform
(Yellow ppt.)
OR
O
C—Cl CHO
(i) Pd/BaSO4
+ H2
OH
½
HCN
(ii) CH3— C— H ¾ ¾ ¾¾® CH3 — C — CN
|| ½
O H
Acetaldehyde cyanohydrin
Conc. KOH
(iii) 2H— C— H ¾ ¾ ¾ ¾ ¾¾® CH3 OH + HCOOK
|| Methanol Potassium methanoate
O
328 Xam idea Chemistry—XII
O H2NCONHNH2
NNHCONH2
(iv) + H2O
– +
COO Na
NaOH, CaO
(v) + Na2CO3
D
SET–II
(Questions Uncommon to Set–I)
1. Glass is an amorphous solid and has a tendency to flow, though very slowly.
2. Due to hydrogen bonding ability of ethylamine.
— C H¾ C H3
4. C H3 ¾ C ¾ C H —
½½ ½
O CH3
6. 5-Chloro-4-methyl pent-1-ene.
7. Is is based on the principle that different components of a mixture are differently adsorbed on an
adsorbent.
8. Ethylene glycol and terephthalic acid
9. Positive deviation.
Minimum boiling azeotropes.
14. CHO
|
HI, D
(a) (CHOH) 4 ¾ ¾ ¾¾® CH3—CH2—CH2—CH2—CH2—CH3
|
n-Hexane
CH2 OH
CHO CH — N — OH
| |
NH 2 OH
(ii) (CHOH) 4 ¾¾¾¾
¾® (CHOH) 4
| |
CH2 OH CH2 OH
16. (i) Kraft temperature is the minimum temperature above which the formation of micelles takes
place.
(ii) Sorption is the process in which adsorption and absorption take place simultaneously, e.g.,
dyeing of cotton fibres by azo dyes.
Examination Papers 329
SET–III
1. 4.
2. 1-chloro 2,4-dinitrobenzene.
3. Caprolactam.
4. The diazonium salts of aromatic amines are more stable than those of aliphatic amines due to dispersal
of the positive charge on the benzene ring.
OH
7. O
8. Vapour phase refining.
9. 0.1 M KCl solution will have higher boiling point as KCl dissociates in the solution.
14. Structural difference between DNA and RNA:
DNA RNA
1. The sugar present in DNA is 2-deoxy D-(–) ribose. 1. The sugar present in RNA is D-(–)-ribose.
2. DNA has double stranded a-helix structure. 2. RNA has single a-helix structure.
330 Xam idea Chemistry—XII
16.
Dispersed phase Dispersion medium
(i) Cheese Liquid Solid
(ii) Fog Liquid Gas
P P
Cl Cl
Cl Cl
Cl Cl
S S Xe
O O O O
OH HO O O
O
26. (i) Aniline to iodobenzene
+ –
NH2 N2Cl I
NaNO2/HCl +KI
273-278 K
Aniline Iodobenzene
zzz
CBSE
Examination
Paper Delhi-2014
Time allowed : 3 hours Maximum marks : 70
General Instructions:
(i) All questions are compulsory.
(ii) Question numbers 1 to 8 are very short answer questions and carry 1 mark each.
(iii) Question numbers 9 to 18 are short answer questions and carry 2 marks each.
(iv) Question numbers 19 to 27 are also short answer questions and carry 3 marks each.
(v) Question numbers 28 to 30 are long answer questions and carry 5 marks each.
(vi) Use log tables, if necessary. Use of calculators is not allowed.
SET–I
1. Give one example each of ‘oil in water’ and ‘water in oil’ emulsion.
2. Which reducing agent is employed to get copper from the leached low grade copper ore?
3. Which of the following is more stable complex and why? [Co(NH3)6]3+ and [Co(en)3]3+
4. Write the IUPAC name of compound.
CH3—CH—CH2—COOH
|
OH
5. Which of the following isomers is more volatile:
o-nitrophenol or p-nitrophenol?
6. What are isotonic solutions?
7. Arrange the following compounds in increasing order of solubility in water:
C6H5NH2, (C2H5)2NH, C2H5NH2
8. Which of the two components of starch is water soluble?
9. An element with density 11.2g cm–3 forms a f.c.c. lattice with edge length of 4 × 10–8 cm.
Calculate the atomic mass of the element.
(Given: NA = 6.022 × 1023 mol–1)
332 Xam idea Chemistry—XII
19. (a) In reference to Freundlich adsorption isotherm write the expression for adsorption of gases on
solids in the form of an equation.
(b) Write an important characteristic of lyophilic sols.
(c) Based on type of particles of dispersed phase, give one example each of associated colloid and
multimolecular colloid.
Examination Papers 333
OR
How will you convert the following:
(i) Nitrobenzene into aniline
(ii) Ethanoic acid into methanamine
(iii) Aniline into N-phenylethanamide
(Write the chemical equations involved.)
28. (a) Define the following terms:
(i) Limiting molar conductivity (ii) Fuel cell
(b) Resistance of a conductivity cell filled with 0.1 mol L–1 KCl solution is 100 W. If the resistance
of the same cell when filled with 0.02 mol L–1KCl solution is 520 W, calculate the conductivity
and molar conductivity of 0.02 mol L–1KCl solution. The conductivity of 0.1 mol L–1KCl
solution is 1.29 × 10–2 W–1 cm–1.
OR
(a) State Faraday’s first law of electrolysis. How much charge in terms of Faraday is required for the
reduction of 1 mol of Cu2+ to Cu?
(b) Calculate emf of the following cell at 298 K:
Mg(s) Mg 2 + (0.1M) Cu 2 + (0.01) Cu(s)
o
[Given E cell = +2.71 V, 1 F = 96500 C mol –1 ]
29. (a) How do you prepare:
(i) K 2 MnO4 from MnO2 ? (ii) Na 2 Cr2 O7 from Na 2 CrO4 ?
(b) Account for the following:
(i) Mn2+ is more stable than Fe2+ towards oxidation to +3 state.
(ii) The enthalpy of atomisation is lowest for Zn in 3d series of the transition elements.
(iii) Actinoid elements show wide range of oxidation states.
OR
(i) Name the element of 3d transition series which shows maximum number of oxidation states.
Why does it show so?
(ii) Which transition metal of 3d series has positive E o (M 2 + / M) value and why?
(iii) Out of Cr3+ and Mn3+, which is a stronger oxidising agent and why?
(iv) Name a member of the lanthanoid series which is well known to exhibit +2 oxidation state.
(v) Complete the following equation:
MnO-4 + 8H+ + 5e - ¾ ¾
¾®
30. (a) Write the products of the following reactions:
H+
(i) O + H2N — OH ¾ ¾¾®
(ii) 2C 6 H5 CHO + conc. NaOH ¾ ¾
¾®
Cl 2 / P
(iii) CH3 COOH ¾ ¾ ¾¾®
(b) Give simple chemical tests to distinguish between the following pairs of compounds:
(i) Benzaldehyde and Benzoic acid
(ii) Propanal and Propanone
Examination Papers 335
OR
(a) Account for the following:
(i) CH3CHO is more reactive than CH3COCH3 towards reaction with HCN.
(ii) Carboxylic acid is a stronger acid than phenol.
(b) Write the chemical equations to illustrate the following name reactions:
(i) Wolff-Kishner reduction
(ii) Aldol condensation
(iii) Cannizzaro reaction
Solutions
SET–I
1. Oil in water emulsion: milk, vanishing cream.
Water in oil emulsion: Butter, cold cream, cod liver oil.
2. Scrap iron, Cu 2 + ( aq) + Fe ( s) ¾ ¾
¾® Cu( s) + Fe 2 + ( aq)
or H2 gas, Cu 2 + ( aq) + H2 ( g) ¾ ¾
¾® Cu( s) + 2H+ ( aq)
3. In both of the given complexes, Co is in +3 oxidation state. As ethane-1, 2-diamine is bidentate
chelating ligand, it forms rings and hence [Co(en)3]3+ is more stable complex than [Co(NH3 ) 6 ] 3 + .
4. 3-hydroxybutanoic acid
5. o-nitrophenol, is more volatile as intermolecular hydrogen bonding causes association molecules in
p-nitrophenol.
O O O O
N H H O N O H O N O
O
p-nitrophenol
o-nitrophenol
Intramolecular hydrogen bonding Intermolecular hydrogen bonding
6. Two solutions which have the same osmotic pressure at a given temperature are called isotonic solutions.
7. The solubility increases in the order in which molecular mass decreases with increase in hydrogen
atoms on nitrogen atom which undergo hydrogen bonding, i.e.,
C 6 H5 NH2 < (C 2 H5 ) 2 NH < C 2 H5 NH2
8. Amylose is water soluble whereas amylopectin is water insoluble component.
9. For fcc lattice number of atoms per unit cell, z = 4
Here, d = 11.2 g cm–3, a = 4 ´ 10 -8 cm, NA = 6.022 × 1023 mol–1
d ´ a3 ´ NA
Atomic mass, M =
z
11.2 g cm -3 ´ ( 4 ´ 10 -8 cm) 3 ´ 6.022 ´ 10 23 mol -1
= = 107.9 g mol–1 or 107.9 u
4
10. (i) Schottky defect
(ii) Decreases
(iii) This type of defect is shown by ionic compounds which have high coordination number and
small difference in size of cations and anions e.g. NaCl, KCl etc.
11. Here, DTf = 0.48 K, MB = 256 g mol–1, WA = 75 g, Kf = 5.12 K kg mol–1.
DTf ´ M B ´ WA 0.48 K ´ 256 g mol -1 ´ 75 g
Mass of solute, WB = = = 1.8 g
K f ´ 1000 5.12 K kg mol –1 ´ 1000 g kg –1
338 Xam idea Chemistry—XII
12. A solution which obeys Raoult’s law over the entire range of concentration is called ideal solution.
The important characteristics of an ideal solution are
(i) The enthalpy of mixing of pure components to form the solution is zero i.e., D mix H = 0
(ii) The volume of mixing is zero i.e., D mix V = 0
13. Differences between order and molecularity of reaction.
Order Molecularity
(i) It is the sum of the powers of the concentration (i) It is the number of reacting species taking part
of the reactants in the rate law expression. in an elementary reaction, which must collide
simultaneously so as to result into a chemical
reaction.
(ii) It is determined experimentally. (ii) It is a theoretical concept.
(iii) It can be zero or a fraction. (iii) It cannot be zero or a fraction.
(iv) Order is applicable to elementary as well as (iv) Molecularity is applicable only for elementary
complex reactions. reactions. For complex reactions it has no
meaning.
(Any two)
14. (i) Zone refining method is based on the principle that the impurities are more soluble in the melt
than in the solid state of the metal.
(ii) Chromatographic method is based on the principle that different components of a mixture are
adsorbed to different extent on an adsorbent. The adsorbed components are removed by using
suitable solvents.
15. (i) Ca 3 P2 ( s) + 6H2 O(l) ¾¾® 2PH3 + 3Ca(OH) 2
(ii) Cu + 2H2SO4(conc.) ¾ ¾
¾® CuSO4 + SO2 + 2H2O
OR
(i) Shorter the bond length, higher is the bond dissociation enthalpy of hydrogen halide. As the
atomic size increases down the group the E–H (E = F, Cl, Br, I) bond length increases and
hence the bond dissociation enthalpy increases in the reverse order i.e.,
HI < HBr < HCl < HF
(ii) H2O < H2S < H2Se < H2Te
The increase in acidic character from H2 O to H2 Te is due to decrease in bond enthalpy for
dissociation of H - E (E = O, S, Se, Te) bond down the group.
16. [Cr(NH3 ) 4 Cl 2 ] + : Tetraamminedichloridochromium (III) ion.
Geometrical isomerism
Cl + Cl +
Cr Cr
Br , primary halides undergo faster S N 2 reactions than secondary halides due to less
steric hinderance.
(ii) (a) SN2 reaction occurs with inversion of configuration.
(b) SN1 reaction occurs with racemisation.
Peroxide
(ii) CH2 CH CH2 + H Br CH2 CH2 CH2 Br
19. (a) Freundlich adsorption isotherm equation for adsorption of gases on solids:
x
= kp1 / n ( n > 1)
m
x 1
or log = log k + log p
m n
where x is the mass of the gas adsorbed on mass m of the adsorbent at pressure p, k and n are
constants which depends on the nature of the gas and adsorbent at a particular temperature.
(b) Important characteristics of lyophilic sols:
(i) They are reversible in nature, i.e., once the dispersed phase is separated from dispersion
medium the sol can be made again by simply remixing with dispersion medium.
(ii) They are quite stable and are not easily coagulated.
(c)
Type of Colloid Example
O O
20. (a) (i) (ii)
F F
Xe S
OH O
F F
OH
XeOF4 H2SO4
Square pyramidal Sulphuric acid
(b) White phosphorus consists of discrete tetrahedral P4 molecule with six P—P covalent bonds.
P
60°
P P
P
340 Xam idea Chemistry—XII
Red phosphorus has polymeric structure in which P4 tetrahedra are linked together through P—P
covalent bond to form chain.
P P P
—P P —P P—P P—
P P P
21. (i) The oxidation state of central atom phosphorus is +5 in PCl5 whereas it is +3 in PCl3. Higher the
positive oxidation of central atom, more will be its polarising power which, in turn, increases the
covalent character of bond formed between the central atom and the atoms surrounding it.
(ii) Iron reacts with HCl to form FeCl2 and H2.
Fe + 2HCl ¾ ¾ ¾® FeCl2 + H2
H2 thus produced prevents the oxidation of FeCl2 to FeCl3.
(iii) Ozone is a resonance hybrid of the following two main structures:
O O
O O O O
As a result of resonance, the two O—O bond lengths in O3 are equal.
2 .303 P0
22. k = log
t 2P0 - Pt
Here, P0 = 0 . 4 atm, t = 100 s, Pt = 0.7 atm
2 . 303 0. 4
\ k = log
100 2 ´ 0 . 4 - 0 .7
2 . 303 0 . 4 2 . 303 2 .303
= log = log 4 = ´ 0 . 6021
100 0 .1 100 100
k = 1.386 ´ 10 -2 s -1
23. (i) Biological macromolecules such as carbohydrates, proteins, lipids and nucleic acids are chosen
as drug targets.
(ii) Antiseptics are the chemical substances which prevent the growth of microorganism or may
even kill them but are not harmful to living human tissues, e.g., dettol, soframycin, boric acid,
hydrogen peroxide etc.
(iii) Use of aspartame is limited to cold foods and soft drink because it is unstable at cooking temperature.
24. (i) Vitamin A
(ii) Uracil
(iii) It suggests that all the six carbon atoms in glucose are linked in a straight chain.
25. (i) Concern towards water pollution, concern for environmental protection, team work, socially aware.
(ii) The polymers which can be broken into small segments by enzyme catalysed reactions or to
some extent by oxidation over a period of time are called biodegradable polymers. The required
enzymes are produced by microorganism e.g., poly-b-hydroxybutyrate-co-b-hydroxyvalerate
(PHBV), nylon-2-nylon-6 etc.
(iii) Polyethene is an addition polymer.
Examination Papers 341
CH3 –
CH3 +
– + d d
(ii) Br + CH2–OH2 Br…CH2…OH2 Br–CH2–CH3 + H2O
Transition state Ethyl bromide
–+ –+
OH ONa ONa OH
CHCl2 CHO CHO
CHCl3 + NaOH (aq) NaOH H+
(b)
Salicylaldehyde
Phenol
Intermediate
OR
NO2 NH2
Sn/HCl(conc)
(i) + 6(H) + 2H2O
Nitrobenzene Aniline
NH3 Br /NaOH
(ii) CH3COOH CH3CONH2 2 CH3NH2
D
Ethanoic acid Ethanamide Methanamine
O
NH2 O
NH—C—CH3
(iii) + CH3—C
O + CH3—COOH
Aniline CH3—C
N–phenylethanamide
O
Ethanoic anhydride
or
O
NH2 O NH—C—CH3
Pyridine
+ CH3—C—Cl + HCl
28. (a) (i) The molar conductivity when concentration approaches to zero is called limiting molar
conductivity.
(ii) A fuel cell is a device which converts energy produced during the combustion of fuels like
hydrogen, methane, methyl alcohol etc. directly into electrical energy. One such successful
fuel cell is hydrogen-oxygen fuel cell.
(b) For 0.1 mol L–1 KCl solution
Conductivity, k = 1.29 × 10–2 W–1 cm–1, Resistance, R = 100 W
Cell constant = Conductivity × resistance
= 1.29 × 10–2 W–1 cm–1 × 100 W = 1.29 cm–1
For 0.02 mol L–1 solution
Resistance = 520 W, Cell constant = 1.29 cm–1,
Cell constant
Conductivity, k =
Resistance
1.29 cm -1
= = 0.00248 W–1 cm–1
520 W
Conductivity ( k) ´ 1000 cm 3 L-1
Molar conductivity, L m =
Molarity
0.00248 W -1 cm -1 ´ 1000 cm 3 L-1
=
0.02 mol L-1
= 124 W -1 cm 2 mol -1
OR
(a) It states that the amount of chemical reaction which occurs at any electrode during electrolysis
by a current is proportional to the quantity of electricity passed through the electrolyte (solution
or melt).
Cu 2 + + 2e – ¾® Cu
Charge required for reduction of 1 mol of Cu2+ = 2F.
(b) At anode: Mg ¾® Mg 2 + + 2e –
At cathode: Cu 2 + + 2e – ¾® Cu
2+
Mg + Cu ¾® Mg 2 + + Cu
o 0.059 [Mg 2 + ]
Nernst equation: Ecell = E cell – log (at 298K)
n [Cu 2 + ]
o
Here, E cell = 2.71 V, [Mg2+] = 0.1 M, [Cu2+] = 0.01 M, n = 2
0.059 01
.
\ Ecell = 2.71 - log = 2.71 - 0.029 ´ 1
2 0.01
= 2.681 V
29. (a) (i) Pyrolusite is fused with KOH in the presence of atmospheric oxygen to give K 2 MnO4 .
Heat
2MnO2 + 4KOH + O2 ¾ ¾ ¾¾® 2K2MnO4 + 2H2O
Pyrolusite Potassium manganate
(ii) Na 2 CrO4 is extracted with water and acidified with H2 SO4 to give Na2Cr2O7.
2Na 2 CrO4 + H2 SO4 ¾ ¾
¾® Na 2 Cr2 O7 + Na 2 SO4 + H2 O
Sodium chromate Sodium dichromate
Examination Papers 343
(b) (i) The electronic configuration of Mn 2 + is [Ar] 3d5 which is half-filled and hence stable. So
Mn 2 + cannot lose third electron easily. On the other hand, Fe 2 + has electronic
configuration [Ar] 3d6. It tends to lose one electron to acquire stable [Ar] 3d5 electronic
configuration. Hence Mn2+ is more stable than Fe2+ towards oxidation.
(ii) In the formation of metallic bonds, no electrons from 3d-orbitals are involved in case of
zinc, while in all other metals of the 3d series, electrons from the d-orbitals are always
involved in the formation of metallic bonds. That is why, the enthalpy of atomisation of
zinc is the lowest in the series.
(iii) This is due to comparable energies of 5f, 6d and 7s orbitals.
OR
(i) Manganese (3d 5 4s 2 ) shows maximum number of oxidation states as its atoms have 5 unpaired
electrons in 3d orbitals. It shows all the oxidation states from +2 to +7.
(ii) Copper has positive Eo (M2+/M) value, as high energy ( D a H + Di H ) to transform Cu(s) to
Cu2+(aq) is not balanced by hydration enthalpy.
(iii) Mn3+ is stronger oxidising agent as the charge from Mn3+ to Mn2+ results in half filled, d5
configuration which has extra stability.
(iv) Europium, Eu. Eu2+ is formed by losing the two s electrons and its (Xe) f 7 configuration accounts
its formation.
(v) MnO-4 + 8H+ + 5e - ¾ ¾
¾® Mn 2 + + 4H2 O
H+
30. (a) (i) O + H2N–OH N–OH + H2O
Cyclohexanone
oxime
– +
(ii) 2C6H5CHO + NaOH C6H5 – CH2 – OH + C6H5COO Na
(Conc.) Benzyl alcohol Sodium benzoate
Cl2/P
(iii) CH3COOH Cl – CH2 – COOH + HCl
2-chloro
ethanoic acid
(b) (i) Benzoic acid being an acid reacts with NaHCO3 solution to give brisk effervescence due
to evolution of CO2 while benzaldehyde does not response to this test.
COOH COONa
(ii) Propanal being an aldehyde reduces Tollens reagent to silver mirror but propanone being a
ketone does not.
CH3CH2CHO + 2[Ag(NH3)2]+ + 3OH – CH3CH2COO– + 2Ag + 4NH3 + 2H2O
Propanal Silver
mirror
344 Xam idea Chemistry—XII
Tollens reagent
CH3COCH3 No silver mirror
Propanone
OR
(a) (i) The methyl group due to its +I effect reduce the magnitude of positive charge on carbonyl
carbon atom. Moreover it also hinders the approach of nucleophile CN- . Since in
acetaldehyde there is one methyl while in acetone there are two methyl groups attached to
carbonyl group therefore acetaldehyde is more reactive than acetone towards nucleophilic
addition with HCN.
(ii) Because the release of proton from carboxylic acid is much easier than from phenol as the
conjugate base carboxylate ion is much more resonance stabilised than conjugate base
phenoxide ion.
(b) (i) Wolff–Kishner reduction
D — CH ¾ CHO
¾ ¾ ¾¾® CH3 ¾ CH —
- H 2O
But - 2 - enal
O O OH O
½½ ½½ Ba (OH) 2 ½ ½½
CH3 ¾ C + H ¾ CH2 ¾ C ¾ CH3 r CH3 ¾ C ¾ CH2 ¾ C ¾ CH3
| Acetone ½
CH3 CH3
4 - Hydroxy - 4 - methyl
- pentan - 2 - one
(Ketol)
O
½½
D
¾ ¾ ¾¾® CH3 ¾ C —
— CH ¾ C ¾ CH3
- H 2O
½
CH3
4 - methylpent - 3 - ene - 2 - one
Examination Papers 345
SET–II
1. Sol: Paints, cell fluids
Gel: Butter, cheese
3. 3-aminobutanal
5. Azeotropes are the binary mixtures of liquids having the same composition in liquid and vapour phase
and boil at a constant temperature e.g. a mixture of 68% nitric acid and 32% water by mass.
6. C 6 H5 NH2 < C 6 H5 NHCH3 < C 6 H5 CH2 NH2
7. Amylopectin
9. It states that “the partial pressure of the gas in vapour phase (p) is directly proportional to the mole
fraction of gas (x) in the solution”.
Mathematically, p = KHx
where KH is the Henry's law constant.
The solubility of a gas in liquid decreases with rise in temperature as dissolution of a gas in a liquid is
an exothermic process.
10. (i) A reaction which is not truely of first order but under certain conditions becomes a reaction of
first order is called pseudo first order reaction e.g. acid hydrolysis of ethyl acetate.
H+
CH3 COOC 2 H5 + H2 O ¾¾® CH3 COOH + C 2 H5 OH
Rate µ [CH3 COOC 2 H5 ] as H2 O is in excess.
(ii) The half life (t ½ ) of a reaction is the time in which the concentration of reactant is reduced to
one half of its initial concentration [R]o.
0.693
For a first order reaction t ½ = i.e., independent of [R]o.
k
[R] o
For a zero order reaction t ½ = i.e., t ½ µ [ R] o .
2k
11. (i) Hydraulic washing: It is based on the differences in the gravities of the ore and the gangue
particles.
(ii) Vapour phase refining: In this, metal is converted into its volatile compound and collected
elsewhere. It is then decomposed to give pure metal. So, the two requirements are:
(a) The metal should form a volatile compound with an available reagent.
(b) The volatile compound should be easily decomposable, so that the recovery is easy.
346 Xam idea Chemistry—XII
22. (a) (i) There are two bond pairs and three lone pairs of electrons around central Xe atom in XeF2.
Therefore according to VSEPR Theory XeF2 should be linear.
F
Xe
(ii) There are three bond pairs and two lone pairs of electrons around central Br atom in BrF3.
Therefore according to VSEPR theory BrF3 should be slightly bent “T”.
F
Br F
24. (i) Due to inert pair effect +3 oxidation state of Bi is more stable than its +5 oxidation state while
+5 oxidation state of Sb is more stable than its +3 oxidation state. Therefore, Bi (V) can more
easily accept a pair of electrons to form more stable Bi (III) than Sb (V) can accept a pair of
electrons and hence Bi (V) is stronger oxidising agent than Sb (V).
(ii) N–N single bond is weaker than P–P single bond due to large interelectronic repulsion between
the lone pairs of electrons present on the N atoms of N–N bond having small bond length.
(iii) Noble gases being monoatomic have no interatomic forces except weak London or dispersion
forces and therefore, they are liquefied at very low temperatures. Hence, they have very low
boiling points.
25. (i) Saccharin, sucrolose.
(ii) Antibiotics are the chemical substance produced wholly or partly by chemical synthesis, which in
low concentrations, either kill or inhibit the growth of microorganisms by intervening in their
metabolic processes. A few examples of antibiotics are chloramphenicol, ofloxacin, penicillin.
(iii) Biomolecules such as carbohydrates, proteins, lipids and nucleic acids are chosen as drug
targets.
27. (i) Vitamin D
(ii) Fibrous protein — keratin, myosin
Globular protein — insulin, albumins
(iii) CHO Br2 water
COOH
| |
(CHOH)4 (CHOH)4
| |
CH2OH CH2OH
D-Glucose Gluconic acid
Examination Papers 347
SET–III
1. Lyophobic sol — Gold sol, As2S3 sol
Lyophilic sol — Sol of starch, sol of gum
2. 4-hydroxypentan-2-one
3. Hydrogen bonds
5. C6H5NH2 < C6H5NHCH3 < C6H5N (CH3)2
H+
6. C12 H22 O11 + H2 O ¾ ¾¾® C 6 H12 O6 + C 6 H12 O6
Sucrose D -(+) - Glucose D -(–) - Fructose
9. It states that for a solution of volatile liquids, the partial vapour pressure of each component in the
solution is directly proportional to its mole fraction. According to Raoults law, for a volatile
component, A of the solution
PA µ x A or PA = PAo x A , where PA0 is the vapour pressure of pure component A.
If one of the component is so volatile that it exist as a gas then according to Henry’s law
p = K H x , where KH is the Henry law constant i.e., the partial vapour pressure of the volatile
component (gas) is directly proportional to its mole fraction in the solution.
Thus the similarity between Raoult’s law and Henry’s law is that both state that the partial vapour
pressure of the volatile component or gas is directly proportional to its mole fraction in the solution.
10. (i) Rate constant, k may be defined as the rate of reaction when concentration of each reactant is
taken as unity.
(ii) Refer to Ans. 10 (ii) Set-II CBSE Delhi 2014.
11. (i) This method of concentration of ore is based on the principle that the surface of sulphide ores is
preferentially wetted by oils while that of gangue is preferentially wetted by water.
(ii) Electrolytic refining: In this method, impure metal is made to act as anode. A strip of same
metal in pure form is used as cathode. They are put in a electrolytic bath containing soluble salt
of same metal. On passing electric current, metal ions from the electrolyte solution are
deposited at the cathode in the form of pure metal while an equivalent amount of metal
dissolves from the anode and goes into the electrolyte solution as metal ions, i.e.,
At cathode: M n + ( aq) + ne – ¾ ¾ ¾® M( s)
At anode: ¾® M n + ( aq) + ne –
M( s) ¾ ¾
The voltage applied for the electrolysis is such that the impurities of more electropositive
metals remain in the solution as ions where impurities of less basic metals settle down under
the anode as anode mud. A large number of metals such as copper, gold, silver, zinc,
aluminium, etc., are refined by this method.
20. (a) (i) There are four bond pairs and two lone pairs of electrons around F F
central Xe atom in XeF4. Therefore according to VSEPR theory
XeF4 should be square planar. Xe
(ii) O O O F F
O O O
N N N N
O O (XeF4) Square planar
O O
(N2O5)
348 Xam idea Chemistry—XII
22. (i) In vapour form sulphur partly exists as S2 molecules which have two unpaired electrons in the
antibonding p * molecular orbitals like O2 molecule and hence, exhibits paramagnetism.
(ii) The oxidation of central atom Sn is +4 in SnCl4 while it is +2 in SnCl2. Higher the positive
oxidation of central atom, more will be its polarising power which, in turn increases the
covalent character of bond formation between the central atom and the atoms around it.
(iii) Acids which contains P—H bonds have reducing character. Since H3PO2 contains two P—H
bonds while H3PO3 contains only one P—H bond therefore H3PO2 is a stronger reducing agent
than H3PO3.
23. (i) Chemical substances which kill microorganisms or stop their growth but are not safe to be
applied to the living tissues are called disinfectants. For example, chlorine in concentrations of
0.2 to 0.4 ppm is used for sterilisation of water to make it fit for drinking.
(ii) Biomolecules such as carbohydrates, proteins, liquids and nucleic acids are chosen as drug targets.
(iii) Anionic detergents: These are so named because large part of their molecules are anions and it
is the anionic part of the molecule which is involved in the cleansing action. These are sodium
salt of sulphonated long chain alcohols or hydrocarbons. For example, sodium lauryl sulphate,
sodium dodecylbenzene sulphonate, etc. Anionic detergents are used in household work and in
toothpastes.
24. (i) Vitamin C
(ii) Peptide linkage
(iii) On prolonged heating with HI, glucose gives n-hexane.
CHO
| HI
(CHOH) 4 ¾ ¾¾® CH3 CH2 CH2 CH2 CH2 CH3
| D n - Hexane
CH2 OH
zzz
CBSE
Examination
Paper All India-2014
Time allowed : 3 hours Maximum marks: 70
SET–I
1. What is the effect of temperature on chemisorption?
2. What is the role of zinc metal in the extraction of silver?
3. What is the basicity of H3PO3?
4. Identify the chiral molecule in the following pair:
Cl
Cl
5. Which of the following is a natural polymer?
Buna-S, Proteins, PVC
6. The conversion of primary aromatic amines into diazonium salts is known as __________ .
7. What are the products of hydrolysis of sucrose?
8. Write the structure of p-methylbenzaldehyde.
9. An element with density 2.8 g cm–3 forms a f.c.c. unit cell with edge length 4 × 10–8 cm. Calculate
the molar mass of the element.
(Given: NA = 6.022 × 1023 mol–1)
10. (i) What type of non-stoichiometric point defect is responsible for the pink colour of LiCl?
(ii) What type of stoichiometric defect is shown by NaCl?
OR
How will you distinguish between the following pairs of terms:
(i) Tetrahedral and octahedral voids
(ii) Crystal lattice and unit cell
11. State Kohlrausch law of independent migration of ions. Why does the conductivity of a solution
decrease with dilution?
350 Xam idea Chemistry—XII
12. For a chemical reaction R ® P, the variation in the concentration (R) vs. time (t) plot is given as
t
(i) Predict the order of the reaction.
(ii) What is the slope of the curve?
13. Explain the principle of the method of electrolytic refining of metals. Give one example.
14. Complete the following equations:
(i) P4 + H2O ¾¾
¾®
(ii) XeF4 + O2F2 ¾ ¾
¾®
15. Draw the structures of the following:
(i) XeF2 (ii) BrF3
16. Write the equations involved in the following reactions:
(i) Reimer-Tiemann reaction
(ii) Williamson synthesis
17. Write the mechanism of the following reaction:
HBr
CH3CH2OH ¾ ¾ ¾® CH3CH2Br + H2O
¾
18. Write the name of monomers used for getting the following polymers:
(i) Bakelite (ii) Neoprene
19. (a) Calculate D r G o for the reaction
Mg(s) + Cu2+(aq) ¾¾
¾® Mg2+(aq) + Cu(s)
o
Given: E cell = +2.71 V, 1 F = 96500 C mol –1
(b) Name the type of cell which was used in Apollo space programme for providing electrical
power.
20. The following data were obtained during the first order thermal decomposition of SO2Cl2 at a
constant volume:
SO2Cl2 (g) ¾ ¾
¾® SO2(g) + Cl2(g)
1 0 0.4
2 100 0.7
(b) Which halogen compound in each of the following pairs will react faster in SN2 reaction?
(i) CH3Br or CH3I
(ii) (CH3)3 C—C1 or CH3—C1
25. Account for the following:
(i) Primary amines (R-NH2) have higher boiling point than tertiary amines (R3N).
(ii) Aniline does not undergo Friedel–Crafts reaction.
(iii) (CH3)2NH is more basic than (CH3)3N in an aqueous solution.
OR
Give the structures of A, B and C in the following reactions:
Sn + HCl NaNO2 + HCl H O
(i) C6H5NO2 ¾ ¾ ¾ ¾¾® A ¾ ¾ ¾ ¾ ¾ ¾® B ¾ ¾2¾
¾® C
273K
H 2O / H + NH 3
Br +KOH
(ii) CH3CN ¾ ¾ ¾ ¾¾® A ¾ ¾ ¾
¾® B ¾ ¾ 2¾ ¾ ¾
¾® C
D
26. Define the following terms as related to proteins:
(i) Peptide linkage
(ii) Primary structure
(iii) Denaturation
27. On the occasion of World Health Day, Dr. Satpal organised a ‘health camp’ for the poor farmers
living in a nearby village. After check-up, he was shocked to see that most of the farmers suffered
from cancer due to regular exposure to pesticides and many were diabetic. They distributed free
medicines to them. Dr. Satpal immediately reported the matter to the National Human Rights
Commission (NHRC). On the suggestions of NHRC, the government decided to provide medical
care, financial assistance, setting up of super-speciality hospitals for treatment and prevention of
the deadly disease in the affected villages all over India.
(i) Write the values shown by
(a) Dr. Satpal (b) NHRC
(ii) What type of analgesics are chiefly used for the relief of pains of terminal cancer?
(iii) Give an example of artificial sweetener that could have been recommended to diabetic
patients.
352 Xam idea Chemistry—XII
(b) Write the chemical equations to illustrate the following name reactions:
(i) Rosenmund reduction
(ii) Cannizzaro’s reaction
(c) Out of CH3CH2 —CO—CH2—CH3 and CH3CH2—CH2—CO—CH3, which gives iodoform
test?
Solutions
SET–I
1. Chemisorption initially increases then decreases with rise in temperature. The initial increase is due to
the fact that heat supplied acts as activation energy. The decrease afterwards is due to the exothermic
nature of adsorption equilibrium.
2. Zinc acts as reducing agent in the extraction of silver. It reduces Ag + to Ag and itself get oxidised to
Zn 2 + .
2Na[Ag(CN)2] + Zn ¾ ¾ ¾¾® Na2[Zn(CN)4] + 2Ag ¯
3. As H3PO3 contains two ionizable P–OH bonds. Therefore, it is dibasic.
O
P
O OH
OH
H3PO3
4.
Cl
5. Proteins
6. Diazotisation.
7. Sucrose on hydrolysis gives one molecule each of glucose and fructose.
H+
C12 H22 O11 + H2 O ¾ ¾¾® C 6 H12 O6 + C 6 H12 O6
Sucrose Glucose Fructose
8. O
C—H
CH3
p-methylbenzaldehyde
At anode: ¾® M n + ( aq) + ne –
M( s) ¾ ¾
The voltage applied for the electrolysis is such that the impurities of more electropositive metals
remain in the solution as ions whereas impurities of less basic metals settle down under the anode as
anode mud. A large number of metals such as copper, gold, silver, zinc, aluminium, etc., are refined
by this method.
14. (i) P4 + H2O ¾¾
¾® No reaction
(ii) XeF4 + O 2 F2 ¾¾
¾® XeF6 + O2 F
15. (i) There are two bond pairs and three lone pairs electrons around central Xe
atom in XeF2. Therefore according to VSEPR theory XeF2 should be
linear. Xe
F
XeF2
Examination Papers 357
(ii) There are three bond pairs and two lone pairs of electrons around central Br atom in BrF3.
Therefore according to VSEPR theory BrF3 should be slightly bent “T”.
F
Br F
F
BrF3
22. (i) Phosphorus due to presence of d orbitals in its valence shell forms pp - dp multiple bonds. As
a result phosphorus can expand its covalency beyond four. Therefore, phosphorus form
R3P—O in which its covalency is 5. In contrast, nitrogen due to absence of d-orbitals, cannot
form pp - dp multiple bonds and hence cannot expand its covalency beyond 4. Therefore,
(CH3 ) 3 N—O does not exist.
(ii) The size of O atom is smaller as compared to S. Thus when an electron is added to isolated
gaseous O atom, the interelectronic repulsions encountered in the smaller 2p-orbitals of O are
larger than those encountered in the larger 3p-orbitals of S.
As a result less energy is released in case of O than in case of S. Hence oxygen has less electron
gain enthalpy with negative sign than sulphur.
(iii) Acids which contains P–H bonds have reducing character. Since H3PO2 contains two P–H
bonds while H3PO3 contains only one P–H bond therefore H3PO2 is a stronger reducing agent
than H3PO3.
23. (i) Tetraamminedichloridochromium (III) chloride.
(ii) Complex [Co(en)3]3+ shows optical isomerism.
3+ 3+
en en
en en
Co Co
en en
d-Tris-(ethane1,2-diamine) l-Tris-(ethane1,2-diamine)
cobalt (III) cobalt (III)
(iii) In complex [NiCl4]2–, Ni is in +2 oxidation state with the electronic configuration 3d8 4s0. As
Cl– is a weak ligand it cannot pair up the electrons in 3d orbitals therefore [NiCl4]2– is
paramagnetic. In [Ni(CO)4], Ni is in zero oxidation state with the electronic configuration
3d8 4s2. CO is a strong ligand it causes 4s electrons to shift to 3d and pair up 3d electrons.
Since there is no unpaired electron in the complex Ni(CO)4, therefore, it is diamagnetic.
PCl5
24. (a) (i) CH2OH CH2Cl + POCl3 + HCl
(ii) Aniline being a Lewis base reacts with AlCl3 a Lewis acid and catalyst used in Friedel crafts
+ -
reaction to form salt C6H5NH2AlCl3. Due to presence of a +ve charge on N-atom in the salt, the
+
group NH2AlCl3 acts as a strong deactivating group. It reduces the electron density in the
benzene ring as a result of this aniline does not undergo Friedel-crafts reaction.
(iii) The basicity of amine in aqueous solution depends upon the stability of the substituted
ammonium cation. Here the combination of three factors, +ve I effect of CH3 groups, hydrogen
bonding and steric hindrance favour greater stability for ammonium cation of dimethyl amine
than ammonium cation of trimethyl amine. Hence dimethylamine is stronger base than
trimethyl amine.
OR
+ –
(i) NH2 N NCl OH
+ –
A = C6H5NH2 , B = C6H5N2Cl , C = C6H5OH
O O
|| ||
(ii) A = CH3 — C— OH , B = CH3 — C— NH2 , C = CH3 — NH2
Ethanoic acid Ethanamide Methanamine
O
||
26. (i) A peptide linkage is an amide (— C— NH —) linkage formed between —COOH group of one
a-amino acid and —NH2 group of other a-amino acid by loss of a water molecule.
(ii) The specific sequence in which various a-amino acids present in a protein are linked to one
another is called its primary structure. Any change in its primary structure creates a new
protein.
(iii) Denaturation of Proteins: When a protein in its native form is subjected to a change, such as
change in temperature or change in pH, the hydrogen bonds are disturbed. Due to this, globules
unfold and helix get uncoiled and protein loses its biological activity. This is called
denaturation of protein. During denaturation, 2° and 3° structures are destroyed but 1°
structures remain intact, e.g., coagulation of egg while on boiling, curdling of milk, etc.
27. (i) (a) The values shown by Dr. Satpal are concern for the health of others, dedicated towards
work, kind, compassionate.
(b) The values shown by NHRC are responsiveness, having understanding of public health in
rural area, dutiful, caring.
(ii) Narcotic analgesics such as morphine, heroin, codeine are used for the relief of pains of
terminal cancer.
(iii) Saccharin, Sucrolose.
28. (a) (i) Molarity may be defined as number of moles of solute dissolved in one litre of solution.
Moles of solute
Molarity =
Volume of solution (in litre)
(ii) Molal elevation constant may be defined as the elevation in boiling point when one mole
of solute is dissolved in 1000 grams of the solvent.
360 Xam idea Chemistry—XII
WB ´ R ´ T
(b) Osmotic pressure, p =
MB ´ V
15 ´ R ´ T
Osmotic pressure of urea solution =
60 ´ 1
W ´R´T
Osmotic pressure of glucose solution = B
180 ´ 1
As, Osmotic pressure of urea solution = Osmotic pressure of glucose solution
15 ´ R ´ T WB ´ R ´ T
Therefore, =
60 ´ 1 180 ´ 1
15 ´ 180
Mass of glucose, WB = = 45 g
60
OR
(a) A mixture of ethanol and acetone shows positive deviation from Raoults law.
In pure ethanol hydrogen bond exist between the molecules. On adding acetone to ethanol,
acetone molecules get in between the molecules of ethanol thus breaking some of the hydrogen
bonds and weakening molecular interactions considerably. Weakening of molecular
interactions leads to increase in vapour pressure resulting in positive deviation from Raoults
law.
(b) Let the mass of solution = 100 g
\ Mass of glucose = 10 g
Mass of glucose
Number of moles of glucose =
Molar mass
10 g
= = 0.056 mol
180 g mol -1
Mass of solution
Volume of solution =
Density of solution
100 g
= = 83.3 mL
1.2 g mL-1
83.3
= L = 0.083 L
1000
Moles of solute
Molarity =
Volume of solution in litre
0.056 mol
= = 0.67 mol L–1
0.083 L
Mass of solvent, water = 100 g – 10 g = 90 g
90 g
= = 0.09 kg
1000 g kg -1
Moles of glucose
Molality =
Mass of water in kg
0.056 mol
= = 0.62 mol kg–1
0.09 kg
Examination Papers 361
(ii) Cerium, Ce ([Xe] 4f 2 5d0 6s2). Formation of Ce4+ is favoured by its noble gas configuration
([Xe] 4f 0 5d0 6s0).
(iii) MnO–4 + 8H+ + 5e - ¾¾
¾® Mn 2 + + 4H2O
(iv) Mn 3 + (3d4 4s0) has 4 unpaired electrons while Cr3+(3d3 4s0) has 3 unpaired electrons therefore
Mn3+ is more paramagnetic than Cr3+.
30. (a) (i) CH3 pH 9-10
CH3 OH
C—O + HCN C
H H CN
Ethanal Hydrogen cyanide Ethanal cyanohydrin
(ii) CH3 H
+ CH3
C—O + H2N—OH C—N—OH + H2O
H pH 3.5 H
Ethanal Ethanal oxime
O O O
|| | ||
l
dil NaOH
(iii) 2CH3 — C— H CH3 — CH— CH2 — C— H
Ethanal 3 - hydroxybutanal
(Aldol)
O
||
D
¾¾
¾® CH3 — CH = CH — C— H
- H 2O But - 2 - enal
362 Xam idea Chemistry—XII
(b) (i) Phenol gives a violet colour with neutral FeCl3 solution while benzoic acid gives buff
coloured precipitate of ferric benzoate.
¾® [Fe(OC6H5)6]3– + 3H+ + 3HCl
6C6H5OH + FeCl3 ¾ ¾
Violet coloured complex
3C6H5COOH + FeCl3 ¾ ¾
¾® (C6H5COO)3Fe + 3HCl
Benzoic acid Ferric benzoate
(Buff coloured ppt.)
(ii) Propanal being an aldehyde reduces Tollens’ reagent to produce silver mirror but
propanone being a ketone does not.
CH3 CH2 CHO + 2[Ag(NH3 ) 2 ] + + 3OH- ® CH3 CH2 COO- + 2Ag ¯ + 4NH3 + 2H2 O
Propanal Silver
mirror
Tollens' reagent
CH3 COCH3 ¾ ¾ ¾ ¾ ¾ ¾¾® No silver mirror
Propanone
OR
(a) (i) Because of –I effect of Cl atom in ClCH2COOH and +I effect of CH3 group in CH3COOH
the electron density in the O—H bond in ClCH2COOH is much lower than CH3COOH.
As a result O—H bond in ClCH2COOH is much weaker than in CH3COOH therefore
loses a proton more easily than CH3COOH. Hence ClCH2COOH acid is stronger acid
than CH3COOH.
(ii) Carboxylic acids are resonance hybrid of the following structures:
é –
··
ù
ê · ú
·
ê O · O ú
·
·· ··
ê ú
êR ¾ C ¬® R¾ C ú
ê ·· + ú
ê O ¾H O ¾ Hú
·· ··
ê ú
ë I II û
Similarly, a carbonyl group of aldehydes and ketones may regarded as resonance hybrid of
following structures.
+ –
C O C—O
III IV
Because of contribution of structure (IV), the carbonyl carbon in aldehydes and ketones is
electrophilic. On the other hand electrophilic character of carboxyl carbon is reduced due
to contribution of structure (II). As carbonyl carbon of carboxyl group is less
electropositive than carbonyl carbon in aldehydes and ketones therefore carboxylic acids
do not give nucleophilic addition reactions of aldehydes and ketones.
Examination Papers 363
O O
C Cl C H
Pd-BaSO4
+ H2 S
+ HCl
Benzoyl chloride Benzaldehyde
SET–II
1. Adsorption occurs with decrease in entropy i.e., DS is –ve. As DG = DH - TDS and for a process to
be spontaneous DG must be –ve. This can be possible only when DH is –ve for the process i.e.,
adsorption is exothermic.
2. Mond process (Vapour phase refining)
3. NO2 is an odd electron molecule in which N has seven electrons in its valence shell and hence is less
stable. To become more stable by acquiring noble gas configuration having 8 electrons in the valence
shell of N, it undergoes dimerisation to form N2O4.
4. Elastomer
5. Maltose on hydrolysis gives two molecules of glucose.
H+
C12 H22 O11 + H2 O ¾ ¾¾® C 6 H12 O6 + C 6 H12 O6
Maltose D -(+) - Glucose D -(+) - Glucose
Cl O
| ||
6. CH3 — CH— CH2 — C— CH3
4 - chloropentan-2-one
(ii) NaCN is used as depressant in froth floatation process. The role of a depressant is to prevent
one type of sulphide particle from forming the froth with air bubble. For example to separate
lead sulphide (PbS) ore from ZnS, NaCN is used as a depressant as it forms zinc complex,
Na2[Zn(CN)4] on the surface of ZnS thereby preventing it from forming froth. Under these
conditions, only PbS forms froth and hence is separated from ZnS.
4NaCN + ZnS ¾¾
¾® Na 2 [Zn(CN) 4 ] + Na 2 S
Sodium tetracynozincate (II)
F F
Xe
F F
(XeF4) Square planar
(ii) Perchloric acid
H
Cl
O O
O
HClO4
19. (i) The linkage between two monosaccharides through oxygen atom in an oligosaccharide or a
polysaccharide is known as glycosidic linkage.
(ii) Sucrose is dextrorotatory (+ 66.5°) but after hydrolysis it gives an equimolar mixture of
D-(+)-glucose and D-(–)-fructose, which is laevorotatory. This change of specific rotation from
dextrorotation to laevorotation is called inversion of sugar and the mixture obtained is called
invert sugar.
Examination Papers 365
(iii) Carbohydrates which on hydrolysis give two to ten molecules of monosaccharides are called
oligosaccharides e.g., sucrose.
SET–III
1. In milk liquid fat acts as dispersed phase and water acts as dispersion medium.
2. Electrolytic refining
3. N atom in NH3 has one lone pair of electrons which is available for donation. Therefore it acts as a
Lewis base.
5. Nylon
H+
6. C12 H22 O11 + H2 O ¾ ¾¾® C 6 H12 O6 + C 6 H12 O6
Lactose Glucose Galactose
8. COOH
OH
2-hydroxy-benzoic acid
9. (i) C + 2H2SO4(conc.) ¾ ¾
¾® CO2 + 2SO2 + 2H2O
(ii) 2XeF2(s) + 2H2O(l) ¾ ¾
¾® 2Xe(g) + 4HF(aq) + O2(g)
10. (i) (ii) O
S
Xe
OH O
O OH
O
O
H2SO4
Pyramidal
XeO3
11. (i) Tetrafluoroethene
(ii) 1, 3–butadiene and acrylonitrile
13. (i) Ferrimagnetism
(ii) Schottky defect
14. (i) Molar conductivity, L m of a solution at a dilution V is defined as the conductance of all the
ions produced from one gram mole of the electrolyte dissolved in V cm3 of the solution when
the electrodes are one centimetre apart and the area of the electrodes is so large that the whole
of the solution is contained between them.
k ´ 1000
L m = k ´ V or Lm =
Molarity
where k is the conductivity and V is the volume of the solution containing 1 mole of the
electrolyte.
(ii) Secondary batteries are those batteries which can be recharged by passing electric current
through them and hence can be used over again e.g. lead storage battery.
17.
366 Xam idea Chemistry—XII
This method of concentration of ore is based upon the principle that the surface of sulphide ore is
preferentially wetted by oils while that of gangue is preferentially wetted by water. Collectors
enhance the non-wettability of the ore particles in the froth floatation process e.g. pine oil.
23. (i) A nucleotide contains all the three basic components of nucleic acid i.e., a pentose sugar, a
nitrogeneous base and a phosphoric acid. When nucleoside is linked to phosphoric acid at 5’
position of sugar moiety, we get a nucleotide.
O
5' 5'
–
HO— H2C O Base O — P— O— H2C O Base
–
4' 1' O 4' 1'
H H H H
3' 2' H 3' 2' H
H H
OH OH OH OH
Nucleoside Nucleotide
(ii) A pair of stereoisomers such as a-D(+) glucose and b-D-(+) glucose which differ in
configuration only around C1 are called anomers.
(iii) The amino acids which cannot be synthesised in our body and must be obtained through diet
are known as essential amino acids e.g., valine, lysine, histidine.
zzz
CBSE
Examination
Paper Foreign-2014
Time allowed : 3 hours Maximum marks: 70
SET–I
1. What is the function of collectors in the froth floatation process for the concentration of ores?
2. What type of forces are responsible for the occurrence of physisorption?
3. Why is the single N—N bond weaker than the single P—P bond?
4. What type of isomerism is shown by the following complex:
[Co(NH3)6] [Cr(CN)6]
5. Express the relationship between atomic radius (r) and the edge length (a) in the b.c.c. unit cell.
6. Write the IUPAC name of the following compound:
OH
CHO
7. Which of the two is more basic and why?
NH2
CH3NH2 or
8. Name the two components of a-glucose which constitute starch.
9. A solution of Ni(NO3)2 is electrolysed between platinum electrodes using a current of 5.0 ampere for
20 minutes. What mass of nickel will be deposited at the cathode?
(Given: At. Mass of Ni = 58.7 g mol–1, 1 F = 96500 C mol–1)
10. Define half-life of a reaction. Write the expression of half-life for
(i) zero order reaction and
(ii) first order reaction.
11. Write the chemical reactions involved in the extraction of silver from silver ore.
12. Name the two most important allotropes of sulphur. Which one of the two is stable at room
temperature? What happens when the stable form is heated above 370 K?
368 Xam idea Chemistry—XII
OR
(i) Write the conditions to maximise the yield of H2 SO4 by contact process.
(ii) Why is K a2 << K a1 for H2 SO4 in water?
13. Complete the following equations:
(i) 2MnO-4 + 5S 2 - + 16H+ ¾ ¾
¾®
(ii) Cr2 O72 - + 2OH- ¾ ¾
¾®
14. Write the state of hybridisation, shape and IUPAC name of the complex [CoF6 ] 3 - .
(Atomic no. of Co = 27)
15. Write chemical equations when
(i) ethyl chloride is treated with aqueous KOH.
(ii) chlorobenzene is treated with CH3 COCl in presence of anhydrous AlCl 3 .
16. (a) Which alkyl halide from the following pairs would you expect to react more rapidly by S N 2
mechanism and why?
CH3 — CH2 — CH— CH3 CH3 — CH2 — CH2 — CH2 — Br
|
Br
(b) Racemisation occurs in SN1 reactions. Why?
17. Write the mechanism of the following reaction:
HBr
CH3 CH2 OH ¾ ¾ ¾
¾® CH3 CH2 Br + H2 O
18. Name the reagents used in the following reactions:
(i) Bromination of phenol to 2, 4, 6-tribromophenol
(ii) Butan-2-one to Butan-2-ol
(iii) Friedel–Crafts alkylation of anisole
(iv) Oxidation of primary alcohol to carboxylic acid
19. (i) What type of stoichiometric defect is shown by KCl and why?
(ii) What type of semiconductor is formed when silicon is doped with As?
(iii) Which one of the following is an example of molecular solid:
CO2 or SiO2
(iv) What type of substances would make better magnets, ferromagnetic or ferrimagnetic?
20. (i) Write two advantages of H2 – O2 fuel cell over ordinary cell.
(ii) Equilibrium constant (Kc) for the given cell reaction is 10. Calculate E °cell .
A(s) + B2+(aq) A2+(aq) + B(s)
21. The following data were obtained during the first order thermal decomposition of SO2Cl2 at a
constant volume:
SO2Cl2(g) ¾ ¾
¾® SO2(g) + Cl2(g)
Experiment Time/s–1 Total pressure/atm
1 0 0.4
2 100 0.7
Examination Papers 369
OR
(a) Define the following terms:
(i) Azeotrope
(ii) Osmotic pressure
(iii) Colligative properties
(b) Calculate the molarity of 9.8% (w/w) solution of H2 SO4 if the density of the solution is 1.02 g mL–1.
(Molar mass of H2SO4 = 98 g mol–1)
29. (a) Account for the following:
(i) Bi is a strong oxidizing agent in the +5 state.
(ii) PCl5 is known but NCl5 is not known.
(iii) Iron dissolves in HCl to form FeCl2 and not FeCl3.
(b) Draw the structures of the following:
(i) XeOF4
(ii) HClO4
OR
(a) Draw the structures of the following:
(i) H2S2O8
(ii) Red P4
(b) Account for the following:
(i) Sulphur in vapour state exhibits paramagnetism.
(ii) Unlike xenon, no distinct chemical compound of helium is known.
(iii) H3PO2 is a stronger reducing agent than H3PO3.
30. (a) Write the products formed when ethanol reacts with the following reagents:
(i) CH3MgBr and then H3O+
(ii) Zn-Hg/conc.HCl
(iii) C6H5CHO in the presence of dilute NaOH
(b) Give simple chemical tests to distinguish between the following pairs of compounds:
(i) Benzoic acid and Ethyl benzoate
(ii) Propanal and Butan-2-one
OR
(a) Account for the following:
(i) CH3CHO is more reactive than CH3COCH3 towards reaction with HCN.
(ii) There are two –NH2 groups in semicarbazide (H2NNHCONH2). However, only one is
involved in the formation of semicarbazone.
(b) Write the chemical equation to illustrate each of the following name reactions:
(i) Rosenmund reduction
(ii) Hell-Volhard-Zelinsky reaction
(iii) Cannizzaro reaction
Examination Papers 371
or
CH3
Solutions
SET–I
1. Collectors (e.g., pine oil, xanthates etc.) enhance non-wettability of the ore particles.
2. Van der Waals forces.
3. N—N bond is weaker than P—P bond because of large interelectronic repulsions between lone pairs
of electrons present on the N atom of N—N bond having small bond length.
4. Co-ordination isomerism
3
5. r (atomic radius) = a (edge length of unit cell)
4
6. 2-hydroxybenzaldehyde
7. In CH3 NH2 , the +I effect of —CH3 group makes lone pair of electrons on N-atom more available for
donation. On the other hand in C6H5NH2, the resonance effect causes delocalisation of lone pair of
electrons over benzene ring and makes it less available for donation. Hence, CH3NH2 is more basic
than C6H5NH2.
8. The two component of starch are amylose and amylopectin.
9. Q = I ´ t = 5 A × 20 × 60 s = 6000 C
Ni 2 + + 2e - ¾ ¾
¾® Ni
2 × 96500 C deposit Ni = 58.7 g
58.7 g mol -1
\ 6000 C will deposit Ni = ´ 6000 C = 1.825 g
2 ´ 96500 C mol -1
10. The half life (t ½ )of a reaction is the time in which the concentration of a reactant is reduced to one
half of its initial concentration.
[R ]0
(i) t ½ for a zero order reaction = where [R]0 = initial concentration, k = rate constant
2k
0.693
(ii) t ½ for a first order reaction =
k
11. The chemical reaction involved in the extraction of silver from silver ore are
4Ag( s) + 8NaCN( aq) +2H2 O(l) + O2 ( g) ¾ ¾
¾® 4Na [Ag(CN) 2 ]( aq) + 4NaOH( aq)
Sodium dicyanoargentate (I)
(Soluble complex)
The forward reaction is exothermic and proceed with decrease in number of moles. Therefore,
low temperature (optimum temperature 720 K), high pressure (in practice 2 bar) and use of
catalyst V2O5 to increase the rate of reaction at low temperature are the favourable conditions
for maximum yield of H2 SO4 .
(ii) H2SO4 is a dibasic acid, it ionizes in two steps and has two dissociation constants.
H2 SO4 ( aq) + H2 O (l) r H3 O+ ( aq) + HSO-4 ( aq); K a > 10
HSO-4 ( aq) + H2 O (l) r H3 O+ ( aq) + SO24 - ( aq) ; K a = 1.2 × 10–2
2
K a2 << K a , because the negatively charged HSO-4 ion has much less tendency to donate a
proton to H2 O as compared to neutral H2SO4.
13. (i) MnO-4 + 8H+ + 5e - ¾ ¾
¾® Mn 2 + + 4H2 O] × 2
S2 - ¾ ¾
¾® S + 2e - ] ´ 5
2MnO4 - + 5S 2 - + 16H+ ¾ ¾
¾® 2Mn 2 + + 5S + 8H2 O
(ii) Cl Cl O Cl
O
Anhyd.AlCl3 —C—CH3
+ CH3—C—Cl +
Chlorobenzene Acetyl o-chloro
chloride acetophenone
C—CH3
(Minor)
O
p-chloro
acetophenone
(Major)
16. (a) CH3—CH2—CH2—CH2—Br. Being primary alkyl halide, there would be less steric hinderance.
(b) This is due to the fact that carbocations are the intermediates in S N 1 reactions. Carbocations
being sp2 hybridised are planar species, therefore, the attack of the nucleophile on it occurs from
both the faces (front and rear) with almost equal ease resulting in the formation of 50 : 50 mixture
of two enantiomers i.e., racemic mixture.
17. Refer to Ans. 26 (a) Set-I CBSE Delhi 2014.
18. (i) Aqueous bromine (Br2/H2O)
(ii) Lithium aluminium hydride (LiAlH4 ) or sodium borohydride (NaBH4 ).
(iii) Anhydrous aluminium chloride (anhyd. AlCl3)
Examination Papers 375
(b) In the formation of metallic bonds, no electrons from 3d-orbitals are involved in case of zinc,
while in all other metals of the 3d series, electrons from the d-orbitals are always involved in the
formation of metallic bonds. That is why, the enthalpy of atomisation of zinc is the lowest in the
series.
(c) Ti3+ has one electron in d-orbitals (3d1) which can absorb light in visible region for d–d
transition. Hence, it is coloured in aqueous solution. Sc3+ has no d electron (3d 0), therefore, no
light is absorbed for d–d transition. Hence, it is colourless in aqueous solution.
24. Refer to Ans 27 Set-I CBSE Delhi 2014.
25. (a) The carbohydrates which differ in configuration at the glycosidic carbon (i.e., C1 in aldoses and
C2 in ketoses) are called anomers e.g., a–D-(+)-glucose and b–D-(+)-glucose.
(b) Denaturation of Proteins: When a protein in its native form is subjected to a change, such as
change in temperature or change in pH, the hydrogen bonds are disturbed. Due to this, globules
unfold and helix get uncoiled and protein loses its biological activity. This is called denaturation
of protein. During denaturation, 2° and 3° structures are destroyed but 1° structures remain intact,
e.g., coagulation of egg while on boiling, curdling of milk, etc.
(c) The amino acids which cannot be synthesised in our body and must be obtained through diet are
known as essential amino acids e.g. valine, lysine, histidine.
26. (i) The drugs which interfere with the natural action of histamine by competing with histamine for
binding of receptor where histamine exerts its effect are called anti histamine e.g., brompheniramine,
terfenadine, cetrizine etc.
(ii) Chloramphenicol
(iii) Use of aspartame is limited to cold foods because it is unstable at cooking temperature.
27. (i) Concern towards water pollution, concern for environmental protection, team work, socially
aware.
(ii) The polymers which can be broken into small segments by enzyme catalysed reactions or to
some extent by oxidation over a period of time are called biodegradable polymers. The required
enzymes are produced by microorganism e.g., poly-b-hydroxybutyrate-co-b-hydroxyvalerate
(PHBV), nylon-2-nylon-6 etc.
(iii) Polyethene is an addition polymer.
28. (a) It states that for a solution of volatile liquids, the partial vapour pressure of each component in
the solution is directly proportional to its mole fraction. Thus, for a solution of volatile liquids
A and B, PA µ xA and PB µ xB or PA = PAo x A and PB = PBo x B where PA and PB are partial
vapour pressures, xA and xB are mole fractions, PAo and PBo are vapour pressure of pure
components A and B respectively.
Ideal solution.
(b) The given quantities are:
WB = 10 g, WA = 200 g, K b = 0 .512 K Kg mol–1,
M B = 111 g mol–1
¾® Ca 2 + + 2Cl -
CaCl 2 ¾ ¾
3
On assuming complete dissociating of CaCl2, i = =3
1
i ´ K b ´ WB ´ 1000
Substituting these values in the formula, DTb = , we get
M B ´ WA
Examination Papers 377
(b) (i) H
(ii)
O
O
F F
Xe
F F
Cl
Square pyramidal O O
O
Perchloric acid
OR
(a) (i) (ii) P P P
O O
S S
O O O —P P — P P — P P —
O
OH HO
P P P
(b) (i) In vapour form sulphur partly exists as S2 molecules which have two unpaired electrons in
the antibonding p * molecular orbitals like O2 molecule and hence, exhibits paramagnetism.
(ii) This is due to the following reasons:
He does not have d-orbitals in the valence shell and hence electron cannot be excited to
higher energy levels like in Xe to form bonds.
Ionisation enthalpy of He is sufficiently higher than those of oxygen and fluorine.
(iii) Acids which contains P—H bonds have reducing character. Since H3PO2 contains two
P—H bonds while H3PO3 contains only one P–H bond therefore H3PO2 is a stronger
reducing agent than H3PO3.
30. (a) (i) O OMgBr OH
CH3MgBr H 3O +
CH3—C—H CH3—C—H CH3—CH—CH3
Ethanal CH3 Propan-2-ol
Zn - Hg
(ii) CH3 CHO + 4 [H] ¾ ¾ ¾¾ ¾® CH3 — CH3 + H2 O
Acetaldehyde conc. HCl Ethane
(iii) O OH O
C H CH CH2 C H CH CH CHO
O
dil. NaOH – H2O
+ CH3 C H
Benzaldehyde Ethanal Aldol 3-phenylprop-2-enal
(b) (i) Benzoic acid being an acid reacts with NaHCO3 solution to produce brisk effervescence
due to evolution of CO2 while ethyl benzoate does not give this test.
Examination Papers 379
– +
COOH COONa
OR
(a) (i) The methyl group due to its +I effect reduce the magnitude of positive charge on carbonyl
carbon atom. Moreover it also hinder the approach of nucleophile CN- . Since in
acetaldehyde there is one methyl while in acetone there are two methyl groups attached to
carbonyl group therefore acetaldehyde is more reactive than acetone towards nucleophilic
addition with HCN.
– –
(ii) O O O
+ +
H2N – C – NHNH2 H2N = C – NH–NH2 H2N–C = NH – NH2
Semicarbazide has two –NH2 groups but one of them (i.e., directly attached to C = O) is
involved in resonance as shown above. Thus, electron density on this NH2 group
decreases hence it does not act as a nucleophile. In contrast, the lone pair of electrons on
the other NH2 group (i.e., attached to —NH) is not involved in resonance and hence is
available for nucleophilic attack on the C = O group of aldehydes and ketones.
(b) (i) Rosenmund reduction:
O O
½½ Pd - BaSO
½½
R ¾ C ¾ Cl + H2 ¾¾¾¾¾
¾
4
® R ¾ C ¾ H + HCl
Acyl chloride S Aldehyde
O O
C Cl C H
Pd-BaSO4
+ H2 S
+ HCl
Benzoyl chloride Benzaldehyde
a
( i ) X 2 / Red P
(ii) R ¾ C H2 ¾ COOH ¾ ¾ ¾ ¾ ¾¾® R ¾ CH ¾ COOH ( X = Cl or Br)
Carboxylic acid ( ii ) H 2 O ½
X
a - Halocarboxylic acid
( i ) Cl 2 / Red P
CH3 ¾ COOH ¾ ¾ ¾ ¾ ¾ ¾® Cl ¾ CH2 ¾ COOH
Carboxylic acid ( ii ) H 2 O Chloroacetic acid
380 Xam idea Chemistry—XII
SET–II
1. Zone refining is based on the principle that the impurities are more soluble in melt than in the solid
state of metal.
2. Kraft temperature
3. Order of basic character
BiH3 < SbH3 < AsH3 < PH3 < NH3
4. Ionisation isomerism
Edge length ( a)
5. Atomic radius (r) =
2 2
6. CH3NH2 is more basic than NH3. CH3 group due to its +ve I effect pushes electron towards nitrogen
··
in CH3 NH2 and this makes the unshared electron pair more available for sharing with the proton of
the acid.
Cl
|
7. Chloroprene (CH2 = C - CH = CH2 )
9. (i) Impure nickel when heated in a current of CO forms volatile complex nickel tetracarbonyl,
Ni(CO)4 leaving behind impurities.
330 - 350K
Ni + 4CO ¾ ¾ ¾ ¾ ¾
¾® Ni(CO) 4
The nickel tetracarbonyl complex thus obtained is then heated to a higher temperature so that it
is decomposed to give pure metal.
450 – 470 K
Ni(CO)4 ¾ ¾ ¾¾¾ ¾® Ni + 4CO
(ii) Graphite rod acts as anode and graphite lined iron acts as cathode in the electrometallurgy of
aluminium.
Carbon reacts with oxygen liberated at anode producing CO and CO2 otherwise oxygen
liberated at the anode may oxidise some of the liberated aluminium back to Al2O3.
At Anode: C( s) + O2 - ( melt) ¾ ¾
¾® CO( g) + 2e -
C( s) + 2O2 - ( melt) ¾ ¾
¾® CO2 ( g) + 4e -
At Cathode : Al 3 + (melt) + 3e - ¾ ¾
¾® Al (l)
10. (i) 2MnO4– + 5NO2– + 6H+ ¾ ¾
¾® 2Mn2+ + 5NO3– + 3H2O
(ii) Cr2O72– + 14H+ + 6e– ¾ ¾
¾® 2Cr3+ + 7H2O
11. [Ni(CN)4]2–: Tetracyanonickelate (II) ion, Ni2+ (3d8)
3d 4s 4p
XX XX XX XX XX = Electron pair from CN– ion
dsp2 hybrid
dsp hybridisation in [Ni (CN)4]2– leads to square planar shape.
2
Examination Papers 381
(ii) Br Br Br
Anhyd. AlCl3 CH3
+ CH3—Cl +
o-bromo toluene CH3
(Minor)
p-bromo toluene
(Major)
SET–III
1. Sodium cyanide (NaCN)
2. Associated colloids
4. Linkage isomerism
5. Propane–1, 2, 3-triol
NH2 NH2
6. is stronger base than as CH3 group is electron releasing by +I effect and hyperconjugation
effect.
CH3
7. Enzymes are termed as biocatalysts as they catalyse numerous reactions that occur in the bodies of
animals and plants to maintain life process e.g., invertase, pepsin, urease.
9. (i) When crude zirconium is heated in an evacuated vessel with iodine, volatile ZrI 4 is formed
which vapourises leaving behind impurities. It is then decomposed by heating over a tungsten
filament at 2075K to give pure zirconium.
870 K 2075 K
Zr( s) + 2I 2 ( g) ¾ ¾ ¾¾® ZrI 4 ( g) ¾ ¾ ¾ ¾ ¾ ¾ ¾® Zr( s) + 2I 2 ( g)
Impure Zirconium Tungsten filament Pure
zirconium tetraiodide zirconium
(ii) Copper matte chiefly consist of Cu2S and FeS. In the converter FeS gets converted into FeO.
Silica (SiO2) acts as a flux to remove FeO impurity as FeSiO3 slag.
2FeS + 3O2 ¾¾
¾® 2FeO + 2SO2
382 Xam idea Chemistry—XII
FeO + SiO2 ¾¾
¾® FeSiO3
Impurity Flux Slag
3+
3d 4s 4p
[Co(NH3)6]
XX XX XX XX XX XX XX = Electron pair
(Inner orbital complex) from NH3
d 2sp 3 hybrid
d2sp3 hybridisation in [Co(NH3)6]3+ leads to octahedral shape.
zzz