Examination Corner 373

Instructions:
1) The question paper has Five parts. All parts are compulsory.
2) a) Part - A carries 20 marks. Each question carries 1 mark
b) Part - B carries 06 marks. Each question carries 2 marks
c) Part - C carries 15 marks. Each question carries 3 marks
d) Part - D carries 20 marks. Each question carries 5 marks
e) Part - E carries 09 marks. Each question (problem) carries 3 marks
3) In Part A questions, First Attempted Answer will be considered for awarding marks.
4) Write balanced chemical equations and draw neat labeled diagrams and graphs wherever necessary.
5) Direct answers to the numerical problems without detailed steps and specific unit for final answer will not
carry any marks.
6) Use log tables and simple calculator if necessary (use of scientific calculator is not allowed).

PART - A
I. Select the correct option from the given choices. 1 ×15 = 15
1. Aquatic species are more comfortable in cold water rather than in warm water. This is due to
a) solubility of oxygen is more in warm water.
b) solubility of oxygen is more in cold water.
c) solubility of gases increases with decrease of temperature.
d) both (b) and (c).
Ans: d) both (b) and (c).

2. Which of the following cell was used in Apollo space programme?

a) Mercury cell b) Daniel cell c) H2–O2 Fuel cell d) Dry cell
Ans : c) H2–O2 Fuel cell
3. During electrolysis of aqueous solution of NaCl, the reaction preferred at anode is
a) 2H2O(l) → O2(g) + 4H+(aq) + 4e- b) H2O(l) + e-→ ½ H2(g) + OH-
c) Cl-(aq) → ½ Cl2(g) + e- d) ½ Cl2(g) + e-→ Cl-(aq)
Ans: c) Cl-(aq) → ½ Cl2(g) + e-
4. Order of a reaction is determined by
a) balanced chemical equation b) unbalanced chemical reaction
c) experimental rate expression d) thermo-chemical equation
Ans: c) experimental rate expression
5. Ionic character decreases in the following oxides.
a) Mn2O7> MnO2>MnO b) MnO> MnO2> Mn2O7
c) Mn2O7>MnO> MnO2 d) MnO> Mn2O7> MnO2
Ans: b) MnO> MnO2> Mn2O7
6. The oxidation state of Fe in [Fe(CO)5] is
a) + 2 b) 0 c) + 3 d) + 5
Ans: b) 0

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7. The gases liberated when primary alcohols react with thionyl chloride are
a) SO2 and H2 b) H2 and HCl c) SO2 and HCl d) NO2and H2
Ans: c) SO2 and HCl

8. Phenol molecule is less stable than phenoxide ion because

a) phenol resonance structures have charge separation but not in phenoxide ion.
b) phenoxide ion resonance structures have charge separation but not in phenol.
c) both Phenoxide ion and phenol resonance structures have charge separation
d) both Phenoxide ion and phenol resonance structures do not have charge separation
Ans: a) phenol resonance structures have charge separation but not in phenoxide ion.

9. Glycerol is an example for

a) dihydric alcohol b) dihydric phenol c) trihydric phenol d) trihydric alcohol
Ans: d) trihydric alcohol

10. Tollen’s reagent is a

a) silver nitrate solution b) ammonical silver nitrate solution
c) ammonium nitrate solution d) silver chloride solution
Ans: b) ammonical silver nitrate solution
11. Carboxylic acids exists in dimeric form even in vapour phase due to
a) Hydrogen bond b) peptide bond
c) ionic bond d) metallic bond
Ans: a) Hydrogen bond

12. The state of hybridization of orbitals of nitrogen atom in amines is;

a) sp2 b) sp3 c) sp d) dsp2
Ans: b) sp3
13. Benzene diazonium chloride reacts with phenol to form p-hydroxy azobenzene in
a) acidic medium b) neutral medium
c) basic medium d) both acidic and neutral medium
Ans: c) basic medium

14. Thiamine is a chemical name of;

a) Vitamin A b) Vitamin B1 c) Vitamin C d) Vitamin K
Ans: b) Vitamin B1

15. The nitrogenous base adenine form hydrogen bonding with

a) Thymine b) Cytosine c) Guanine d) None of the above
Ans: a) Thymine
II. Fill in the blanks by choosing the appropriate word from those given in the brackets: 5 × 1 = 05
(phosgene, tin, hydrogen, molecularity, zinc, cellulose acetate)
16. The semi permeable membrane used in the reverse osmosis is ________________.
Ans: cellulose acetate
17. The number of molecules taking part in the elementary reaction is called _______.
Ans: molecularity

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18. The non-transitional metal present in brass is ___________.
Ans: zinc
19. The poisonous gas formed when chloroform is exposed to air and light is ________.
Ans: phosgene
20. Solubility of ethylamine in water is due to formation of _______bonding with water.
Ans: hydrogen
PART - B
III. Answer any three of the following. Each question carries two marks. 3 × 2 = 06
21. How does the boiling point of solvent varies, when a non-volatile solute is dissolved in it? Give reason.
Ans: Boiling point of solvent increases. Because vapour pressure of solvent decreases by adding non volatile
solute.
22. Define order of a reaction. For which order reaction the unit of rate of reaction and rate constant is
same?
Ans: The sum of powers of the concentration of the reactants in the rate law expression is called order of the
reaction.
Zero order.
23. What are chelate ligands? Give an example.
Ans: A di or poly dentate ligand that uses two or more donar atoms to bind a single metal ion is called chelating
ligand. Example: EDTA
24. Write the general equation for Finkelstein reaction. What is the role of dry acetone in this reaction?
Ans:
dry
R X + NaI acetone R I + NaX
Haloalkane Iodoalkane
X = Cl, Br
NaCl or NaBr formed is precipitated in dry acetone to prevent the backward reaction. It facilitates the forward
reaction according to Le Chatelier’s principle.
O

25. Complete the equation and name the reaction: R  C  CH 3  NaOX


O O
 
Ans: R  C  CH 
NaOX
 R  C  ONa  CHX3 (X  Cl, Br, I)
3
Haloform

Name of the reaction – Haloform reaction

26. Name two hormones which regulate the glucose level in the blood.
Ans: (i) Insulin
(ii) Glucagon
PART - C
IV. Answer any three of the following. Each question carries three marks. 3 × 3 = 09
3+
27. Calculate the spin only magnetic moment of M (aq)ion. (Z = 24)
18 4 2
Ans: Z = 24, [Ar] 3d 4s

For M3+ ion: [Ar]18 3d 3 4s0

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 n = 3 (number of unpaired electrons)
  n(n  2)

 3(3  2)

 15
 3.873 B M
28. Explain the structure of dichromate ion (Cr2O72-).
Ans: The dichromate ion consists of two tetrahedra sharing one corner with Cr – O – Cr bond angle of 126o.

29. What is Lanthanoid contraction? Mention two of its consequences.

Ans: The overall decrease in atomic and ionic radii from lanthanum to lutitium is called lanthanoid contraction.
(i) Due to lanthanoid contraction the atomic radii of Zr (160 pm) and Hf (159 pm) is almost same.
(ii) Covalent character of cations increases.
30. Write the IUPAC names and the type of isomerism for the following complexes
(a) [Co(NH3)5Br]SO4 and (b) [Co(NH3)5SO4]Br.
Ans: a) Pentaamminebromidocobalt(III) sulphate
b) Pentamminesulphatocobalt(III) bromide
Ionisation isomerism
31. Using Valence Bond Theory [VBT], explain geometry, hybridisation and magnetic property of [CoF6]-3
ion. [Atomic number of Cobalt is 27].
Ans: In this complex, the oxidation state of Co is +3. The electronic configuration of cobalt in +3 oxidation state
is [Ar]3d64s0.
Orbitals of Co3+ ion are represented as

Since F– ion provides a weak ligand field, one 4s, three 4p and two outer 4d-orbitals hybridised to yield six
sp3d2 hybrid orbitals pointing towards the six corners of an octahedron.
Sp3 d2 hybridised orbitals of Co3+ are as shown below.

3 2
3d sp d hybrid 4d
3
 [CoF6 ] complex is

-
3d six pairs of electrons forms 6F ion 4d

 The type of hybridization is sp3d2. The complex has octahedral geometry. This complex is
paramagnetic because of the presence of unpaired electrons.

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Examination Corner 377
32. Draw the energy level diagram for the crystal field splitting in tetrahedral complexes. Write the relation
between Δ0 and Δt for the complexes having same metal, the same ligand and metal-ligand distances.
Ans:

4
Relation between  o and  t =  t   o
9
V. Answer any two of the following. Each question carries three marks. 2 × 3 = 06
33. Write any three differences between ideal and non-ideal solutions.
Ans:
Sl.
Ideal solution Non-ideal solution
No.
i. They obey Raoult’s law. They do not obey Raoult’s law.
ii. Vmix  0 Vmix  0
iii. H mix  0 H mix  0

34. State Kohlrausch’s law of independent migration of ions. Mention two applications of it.
Ans: It states that the molar conductance of an electrolyte at infinite dilution is equal to the sum of the ionic
conductances of respective cations and anions of electrolyte.
OR
It states that the limiting molar conductivity of an electrolyte can be represented as the sum of the individual
contributions of the anion and cation of the electrolyte.
Applications: Kohlrauch’s law is used
a) to determine the molar conductivity of a weak electrolyte which cannot be determined experimentally.
b) to determine the degree of dissociation ‘’ and the dissociation constant Ka for a weak electrolyte.

35. Explain the experimental determination of conductance of electrolytic solution by using Wheatstone
bridge.
Ans: The determination involves the following two steps.

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Step 1: Determination of cell constant of conductivity cell
Conductivity cell of suitable design is filled with KCl
solution of known specific conductance (). It is
connected to Wheatstone bridge as shown in the figure. R1
is a variable resistance, R2 be the resistance of
conductivity cell, R3 and R4 are two fixed resistances. P is
the detector. The bridge is connected to an A.C. source of
power as shown in figure.
The variable resistance is adjusted such that the detector
shows no current in the circuit and the bridge is balanced.
At this condition the resistance of the conductivity cell is
given by,
R1 R 3 Fig. Arrangement for

R2 R4 measurement of resistance of a
R 1R 4 solution of an electrolyte
 R2 
R3
The cell constant of the conductivity cell is calculated using the relation
G*  R 2  ( is known)
Step 2: Determination of specific conductance of the given electrolyte solution
The conductivity cell is now filled with given electrolytic solution. It is connected to the Wheatstone bridge
and the experiment is repeated. The resistance R2 of the electrolytic solution is determined. Specific
conductance of the electrolytic solution is calculated using the relation,
G*

R2
36. Derive integrated rate equation for first order gas phase reaction.
Ans: Consider a first order gas phase reaction of the type
A(g)   B(g)  C(g)
At t = 0 pi 0 0
At time t, pi  x x x
Where ‘x’ is the decrease in pressure of reactant A at time t and increase in pressure of products B and C. pi
is the initial pressure at time t = 0.
After a time t, total pressure pt = (pi – x) + x + x
p t  pi  x
x  p t  pi
But at a time t, p A  pi  x
p A  pi  (p t  pi )
p A  pi  p t  pi
p A  2pi  p t
In gas phase reactions, first order rate equation can be written by replacing concentration terms with
pressures of gaseous reactants as follows:
2  303 p
k log i
t pA

2  303 pi
 k log
t 2pi  p t

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Examination Corner 379
PART - D
VI. Answer any four of the following. Each question carries five marks. 4 × 5 = 20
37. a) Write the mechanism involved in the following reaction:
(CH3)3CBr + OH– → (CH3)3COH + Br–
Identify the reactant on which rate of reaction depends.
b) Define stereocenter? How many asymmetric carbon atoms are there in 2, 3-dichlorobutane? (3+2)
Ans: Mechanism: It is SN1 mechanism and involves two steps. It follows first order kinetics.
I Step: (slow step): Tertiary butyl bromide ionizes slowly to give sp2 hybridised planar tertiary butyl
carbocation and bromide ion.
CH3 CH3
+
CH3 C Br C + Br
H3C CH3 Slow, rate determining step
CH3
Tertiary butyl bromide Tertiary butyl carbocation

II Step: (Fast step)  The nucleophile OH from aqueous NaOH attacks planar carbocation on either side
to give tertiary butyl alcohol.
CH3 CH3
+
C + OH CH3 C OH
H3 C CH3
CH3
Tertiary butyl alcohol

The product tertiary butyl alcohol obtained is a racemic mixture.

Rate of reaction depends on concentration of tertiary butyl bromide.
b) A carbon atom bonded to four different atoms or groups is called chiral carbon atom or stereo centre.
Cl Cl
| |
CH 3  C  C  CH 3
| |
H H
Number of asymmetric carbon atoms = 2
38. a) Identify A, B and C in the following reaction:
H2SO4
B
443 k
Pd
A + H2 C2H5OH
H2SO4
C
413 K
b) Describe the manufacture of methanol from water gas. (3+2)
Ans: a) A  CH3CHO
Acetaldehyde
B  CH 2  CH 2
Ethene
C  C2 H5  O  C 2 H5
Dietheyl ether

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b) Carbon monoxide gas is mixed with hydrogen (Water gas) and passed over zinc oxide and chromium
trioxide (ZnO-Cr2O3) catalyst at 573K to 673K and 200 to 300atm to give methanol (wood spirit).
ZnO Cr O
CO  2H 2 
2 3
 CH 3OH
200300 atm, 573673 K
Methanol
39. a) An aromatic hydrocarbon ‘A’ having molecular formula C9H12 is oxidised in the presence of air
gives compound ‘B’. The compound ‘B’ is treated with dilute acid gives two organic compounds
‘C’ and ‘D’. The compound ‘C’ forms white precipitate ‘E’ with bromine water. Write the chemical
reactions with names of A, B, C and E.
b) Give an example for unsymmetrical (mixed) ether. (4+1)
Ans: a)
CH3 CH3
CH3 C H H3 C C O O H OH
O
+
O2 H + CH3 C CH3
H2 O
Cumene Cumene Phenol Acetone
(Isopropyl benzene) hydroperoxide
(A) (B) (C) (D)
Phenol reacts with bromine water to give white precipitate of 2,4,6- tribromophenol.
OH OH
Br Br
H2 O
+ 3Br2 + 3HBr

Phenol
Br
2, 4, 6 -Tribromo phenol
(C) (E)
b) Ethyl methyl ether (C2H5 – O – CH3) or Methoxy ethane.
40. a. Write the chemical equation for the reaction when benzaldehyde is slightly heated with
acetophenone in the presence of dilute alkali. Give the IUPAC name of the product.
b. Explain Rosenmund reduction with an example.
c. Alpha (α) -Hydrogens of aldehydes and ketones are acidic. Give reason. (2+2+1)
Ans: a)

IUPAC name : 1, 3-Diphenylprop-2-en-1-one

b) Acid chlorides on reduction with H2 in presence of palladium catalyst supported by barium sulphate give
aldehydes. This reaction is called Rosenmund’s reduction.

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Examination Corner 381
Example

c) The acidity of -hydrogens in carbonyl compounds is due to the strong electron withdrawing effect of the
carbonyl group and resonance stabilization of the conjugate base.

41. a) A Grignard reagent ‘X’ reacts with CO2 (dry ice) followed by acid hydrolysis gives ethanoic acid.
Write the chemical equation. Name the compound ‘X’?
b) Between methanoic acid and ethanoic acid, which is more acidic? Give reason. (3+2)

Ans: a)

b) Methanoic acid (H–COOH) is stronger acid than ethanoic acid. (CH3COOH)

Because, in ethanoic acid, methyl group causes +I effect and decreases the stability of carboxylate ion and
hence acidity decreases.
42. a) Write the chemical name and structure of Hinsberg’s reagent. 3- amines do not react with
Hinsberg’s reagent. Give reason.
b) Explain Carbylamine reaction with an example. (3+2)
Ans: a) Benzene sulphonyl chloride
O

S Cl

O
Due to absence of H-atom on N of 3o amines, they do not react with Hinsberg reagent.
b) When a primary amine is heated with chloroform and alcoholic KOH gives isocyanides called
carbylamines. This reaction is called carbylamine reaction.

R  NH 2  CHCl3  3KOH   R  NC  3KCl  3H 2 O
1° amine Chloroform ( Alcoholic )
isocyanide

Example:

(a) CH3  NH 2  CHCl3  3KOH   CH3  NC  3KCl  3H 2 O
Methanamine Chloroform (Alcoholic) methyl isocyanide

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43. a) (i) The penta-acetate of glucose does not react with Hydroxylamine. What does it indicate?
(ii) Write chemical reaction to show the open chain structure of D-glucose which contains six carbon
atom the straight chain.
b) What is Zwitter ion of an amino acid? Give its general structure.
c) Name the hormone responsible for the hypothyroidism? (2+2+1)
Ans: a) i) Indicates the absence of free aldehyde group in glucose.
ii) Glucose on heating with HI and red phosphorus gives n-hexane. This shows that glucose contains 6
carbon atoms in a straight chain.
HI 
C6 H12 O 6 
Re d P
 CH 3  CH 2  CH 2  CH 2  CH 2  CH 3
Gluc os e (n-Hexane)

b) In aqueous solution, the carboxyl group of amino acid donates a proton and amino group (NH2) can
accept a proton giving rise to a dipolar ion known as Zwitter ion.
H O H O
+
H 2N C C OH H3 N C C O

R R
(Zwitter ion)
c) Thyroxine

PART – E (PROBLEMS)
VII. Answer any three of the following. Each question carries three marks. 3 × 3 = 09
-1
44. 100 g of liquid ‘A’ (molar mass 140 gmol )was dissolved in 1000 g of liquid ‘B’
(molar mass 180 gmol-1). The vapour pressure of liquid ‘B’ was found to be 500 torr. Calculate the
vapour pressure of pure liquid ‘A’ if the total vapor pressure of the solution is 475 torr.
100 1000
Ans: n A   0.7143mol , n B   5.555 mol
140 180
nA 0.7143 0.7413
xA     0.1139
n A  n B 0.7143  5.555 6.2963
xA + xB = 1
xB = 1 – xA
= 1 – 0.1139 = 0.8861
P = p oA xA + p oB xB

475  poA  0.1139  500  0.8861

p oA  0.1139  475  443.05

p oA  0.1139  31.95
31.95
p oA   280.51 torr
0.1139
45. The boiling point of benzene is 353.23K. When 1.8g of non-volatile solute was dissolved in 90g of
benzene, the boiling point is raised to 354.11K. Calculate the molar mass of the solute. (Given Kb for
benzene is 2.53Kkgmol–1).
K b  w B  1000
Ans: M B 
Tb  w A

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Tb  Tb  T  354.11  313.23 = 0.88 K
o
b

2.53  1.8  1000

MB   57.5 g mol1
0.88  90
46. At 298K, the EMF of the cell: Mg(s) |Mg2+(Q)||Ag+(0.01)|Ag(s)is 3.022V. Calculate the value ‘Q’.
(Given: EoMg2+/Mg = -2.37V and EoAg+/Ag = 0.80V).
Ans : Mg(s) | Mg 2 (Q)  Ag  (0.01)Ag(s)

Mg  Mg 2  2e

 
2Ag  2e  2Ag

Mg  2Ag  Mg 2  2Ag
n=2
E o
cell E o
Ag  / Ag
 E oMg2 /Mg

 0.80V  ( 2.37)
= 3.17 V
0.0591 [Mg 2  ]
E cell  E ocell  log
n [Ag  ]2

0.0591 Q
 3.022  3.17  log
2 (0.01)2

0.0591
log Q  104  3.17  3.022
2
0.148  2
log Q  104 
0.0591
log Q  104  5.0084

Q  104  Anti log(5.0084)

Q  104  1.020  105
1.020  105
Q  1.020  101 = 10.20 M
104
47. The resistance of 0.01M acetic acid solution is found to be 2220Ω, when measured in a cell has two
electrodes of area of cross section 3.85cm2 placed 10.5cm apart. Calculate conductivity.
Ans: R  2220 , A  3.85 cm 2   10.5 cm
 10.5
Cell constant (G)    2.7272cm 1
A 3.85
G  2.7272
Conductivity ( )    0.001228 Scm 1
R 2220
48. For a first order reaction, the half-life period is 120 min. Calculate the time required to complete 90%
of the reaction.
0.693 0.693
Ans: k   0.005775 min 1
t1/ 2 120
2.303 [R]o
t log
k [R]

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[R]o  100% , [R]  100  90  10%
2.303 100
t log
0.005775 10
2.303
t log10
0.005775
2.303
t 1
0.005775
t  398.78 min
49. The rate constants of a reaction are 2 × 10-2s1 at 300K and 8 × 10-2 s1 at 320 K. Calculate the energy of
activation of the reaction. (Given: R = 8.314JK-1mol-1).
k2 E a  T2  T1 
Ans: log   
k1 2.303R  T1T2 

8  102 Ea  320  300 

log 
2  10 2
2.303  8.314  300  320 
E a  20
log 4 
2.303  8.314  300  320
E a  20
0.6021 
2.303  8.314  300  320
0.6021  2.303  8.314  300  320
Ea 
20
 55336.77 J  55.336 kJ

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