Prepared by:Prof. S.Narayana Iyer,M.Sc,M.

Phil

GUESS QUESTION paper IN CHEMISTRY FOR XII (ISC) BOARD

EXAMINATION MARCH 2011
Paper – 1
(THEORY)
(Three Hours)
(Candidates are allowed additional 15 minutes for only reading the paper. They must
NOT start writing during this time)
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Answer all questions in Part I and six questions from Part II, choosing two questions
from Section A, two from Section B and two from Section C.
All working, including rough work, should be done on the same sheet as, and adjacent to,
the rest of the answer. The intended marks for questions or parts of questions are given in
brackets [ ]. Balanced equations must be given wherever possible and diagrams where
they are helpful. When solving numerical problems, all essential working must be shown.
In working out problems use the following data: Gas Constant R = 1.987 cal deg-1 mol-1
= 8.314 JK-1 mol-1 = 0.0821 dm3 atm K-1mol-1
1 l atm = 1 dm3 atm = 101.3 J. 1 Faraday = 96500 Coulombs.
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PART I (Answer all questions)
Question 1
a) Fill in the blanks choosing appropriate words given in brackets: [5]
(zero, infinity, twelve, negative, positive, four, six, increases, van’t Hoff’s
factor, does not change, nucleophilic, no alpha, ammoniacal, alpha)

(1) The ratio of observed value of colligative property to the calculated value of
colligative property is called.............................................
(2) The standard reduction potential value of normal hydrogen electrode is.....................
(3) The co-ordination number of Na+ ion in rock salt structure is...........
(4) If the free energy change is ...................the reaction does not proceed in the forward
direction.
(5) Cannizzaro reaction is shown by an aldehyde containing................
hydrogen atom.
Ans: (1) van’t Hoff’s factor (2) zero (3) six (4) positive (5) no alpha

(b) Complete the following statements by selecting the correct alternative from the
choices given: [5]
(1) The pair of sugar which give the same product with excess of phenyl
hydrazine are:
a) starch and cellulose b) cellulose and sucrose
1
c) sucrose and glucose d) glucose and fructose
(2) Mesotartaric acid is optically inactive due to the presence of:
a) Molecular symmetry b) Molecular asymmetry
c) External compensation d) Asymmetric carbon atom
(3) Which of the following is an amorphous solid ?
a) NaCl b) glass c) CaF2 d) graphite
(4) Which of the following is not a carboxylic acid?
a) oxalic acid b) picric acid c) propanoic acid d) formic acid
(5) Benzaldehyde treated with alkaline KMnO4 gives:
a) CO2 and H2O b) benzyl alcohol c) salicylic acid d) benzoic acid
Ans:
(1) d) glucose and fructose (2) a) Molecular symmetry (3) b) glass
(4) b) picric acid (5) d) benzoic acid

(c) Answer the following questions: [5]

(1)Why water cannot be separated completely from ethyl alcohol by fractional
distillation?
Ans.Ethyl alcohol and water (95.4% ethyl alcohol and 4.6% water) form constant boiling
mixture (azeotrope) boiling at 351.1 °K. Hence, further water cannot be separated
completely from ethyl alcohol by fractional distillation.
(2) Which solution will allow greater conductance of electricity, 1 M NaCl at 293 K or 1
M NaCl at 323 K and why ?
Ans. 1 M NaCl at 323 K as the ionic mobilities increase with increase in temperature.
(3) For a reaction A + H2O → B; r = k [A]. What is its (i) Molecularity (ii) Order?
Ans. (i) Pseudo unimolecular reaction (ii) order = 1
(4) Why it is necessary to use a salt bridge in a galvanic cell?
Ans. To complete the inner circuit and to maintain electrical neutrality of the electrolytic
solutions of the half-cells.
(5) Give the relationship between free energy change and EMF of a cell.

Ans.
- ∆G = n FEcell
∆G = Free energy changes n = moles of electrons F = 96500 Coulomb
Ecell = EMF of a cell
2
(d) Match the following:
(i) Benedict’s reagent
(ii) Fehling solution
(iii)Tollen’s reagent
(iv) heating of alkyl halide
and sodium alkoxide
(v) urotropine
Ans:
(i) Benedict’s reagent
(ii)Fehling solution
(iii)Tollen’s reagent
(iv) heating of alkyl halide
and sodium alkoxide
(v) urotropine
[5]
a) ammoniacal silver nitrate
b) Williamson’s synthesis
c) formaldehyde
d) copper slulphate + sodium
potassium tartrate
e) copper sulphate + sodium citrate
e) copper sulphate + sodium citrate
d) copper slulphate + sodium potassium tartrate
a) ammoniacal silver nitrate
b) Williamson’s synthesis
c) formaldehyde

PART II
Answer six questions choosing two from Section A, two from Section B and two from
Section C.
SECTION A (Answer any two questions)
Question 2
(a) An aqueous solution of cane sugar containing 1.72 g in 100 mL begins to freeze
at -0.093oC. The cryoscopic constant of water is 1.86 K mol-1kg-1
Calculate the molecular weight of cane sugar. [3]
Ans.
o o
ΔTf = 0 - (-0.093 ) = 0.093
1000 x 1.86 x 1.72
m = 1000 kf w = = 344
ΔTf W 0.093 x 100
(b) At 300 K, 36 g of glucose present in a litre of its solution has an osmotic pressure of
4.98 bar. If the osmotic pressure of the solution is 1.52 bars at the same temperature, what
would be its concentration? [3]
Ans. Here, T = 300 K π = 1.52 bar R = 0.083 bar L K−1 mol−1
Applying the relation,
π = CRT

3
 π
C =
R T
1.52 bar
C =
0.083 bar L K -1 m ol -1 x 300 K

= 0.061 mol
since the volume of the solution is 1 L, the concentration of the solution would be
0.061M.
(c) Give reasons for the following:
(i) The specific conductivity of a solution decreases with dilution [2]
(ii) Ionic solids conduct electricity in molten state but not in solid state. [2]

(i) Specific conductivity of a solution depends upon number of ions present in per
unit volume. On dilution, the number of ions per unit volume decreases. Therefore the
specific conductivity also decreases.
(ii) In ionic compounds, electricity is conducted by ions. In solid state, ions are held
together by strong electrostatic forces and are not free to move about within the solid.
Hence, ionic solids do not conduct electricity in solid state. However, in molten state or
in solution form, the ions are free to move and can conduct electricity
Question 3
(a) (i) Silver crystallises in fcc lattice. If edge length of the cell is 4.07 × 10−8 cm and
density is 10.5 g cm−3, calculate the atomic mass of silver [3]
Ans.
It is given that the edge length, a = 4.077 × 10−8 cm
Density, d = 10.5 g cm−3
As the lattice is fcc type, the number of atoms per unit cell, z = 4
We also know that, NA = 6.022 × 1023 mol−1

Using the relation:

4
 zM
d=
a3 NA

d a3 NA 10.5 gcm3 x (4.077 x 10-8 cm )3 x 6.023 x 1023

M= = = 107.143
z 4

= 107.143 gmol−1 Therefore, atomic mass of silver = 107.143 u

(ii) What is the total number of sigma and pi bonds in the following molecules?
(a) C2H2 (b) C2H4 [1]
Ans.a) Structure of C2H2 can be represented as:

σ π
σ σ
H C C H
π

Hence, there are three sigma and two pi-bonds in C2H2.

b) The structure of C2H4 can be represented as:

H σ σ
H
σ
C π C
σ σ
H H
Hence, there are five sigma bonds and one pi-bond in C2H4.

(b) (i) Time required to decompose SO2Cl2 to half of its initial amount is 60 minutes. If
the decomposition is a first order reaction, calculate the rate constant of the reaction. [3]
Ans. For a 1st order reaction,

0.693
t1/2 =
k

5
It is given that t1/2 = 60 min

0.693 0.693
k= t 1/ = = 0.01155 min-1
2
60

or k = 1.925 x 10-4 s-1

(ii) The rate of a reaction quadruples when the temperature changes from 293 K to 313 K.
Calculate the energy of activation of the reaction assuming that it does not change with
temperature. [3]

Ans. From Arrhenius equation, we obtain

log
k2 Ea T2 - T1
=
k1 2.303 R T 1T 2
It is given that k 2 = 4k 1

T 1 = 293K
T 2 = 313K
4k 1 Ea 313 - 293
log =
k1 2.303 x 8.314 293 x 313
20 x Ea
0.6021 =
2.303 x 8.314 x 293 x 313
0.6021 x 2.303 x 8.314 x 293 x 313
Ea = = 52863.33J mol-1
20
= 52.86kJmol-1

Hence, the required energy of activation is 52.86 kJmol−1.

Question 4
(a) (i) Although geometries of NH3 and H2O molecules are distorted tetrahedral, bond
angle in water is less than that of ammonia. Discuss. [2]

6
Ans. The molecular geometry of NH3 and H2O can be shown as:

N O
H H H H
H
The central atom (N) in NH3 has one lone pair and there are three bond pairs. In H2O,
there are two lone pairs and two bond pairs.
The two lone pairs present in the oxygen atom of H2O molecule repels the two bond
pairs. This repulsion is stronger than the repulsion between the lone pair and the three
bond pairs on the nitrogen atom.
Since the repulsions on the bond pairs in H2O molecule are greater than that in NH3, the
bond angle in water is less than that of ammonia.

(ii) Calculate the pH of a buffer solution containing 0.01 mole of acetic acid and 0.015
mole of sodium acetate. Ka of acetic acid is 1.75 x 10-5 [3]
Ans.

[salt]
pH = - log Ka + log
[acid]
[0.15]
pH = - log 1.75 x 10-5+ log
[0.1]
pH = - 4.756962 + 0.1761 = 4.933

b) Give reasons why: [5]

(i) Example 1: Calculate the standard e.m.f. of the cell : Cd, Cd2+ || Cu2+,Cu and
determine the cell reaction. The standard reduction potentials of
Cu2+, Cu and Cd2+, Cd are 0.34V and –0.40 volts respectively. Predict the
feasibility of the cell reaction.
Eocell = Standard EMF of the cell = Eoright – Eoleft
= [Std. reduction potential of Cu2+, Cu] – [Std. reduction potentials of Cd2+, Cd]
= EoCu2+, Cu – EoCd2+, Cd
= 0.34 V – (– 0.4 V)
= + 0.74 Volts.
Left hand electrode (oxidation half cell) reaction is
7
Cd(s) → Cd2+ + 2e
Right hand electrode (reduction half cell) reaction is
Cu2+ + 2e → Cu(s)
The cell reaction is
Cd(s) + Cu2+(aq) → Cd2+(aq) + Cu(s)
Eocell is positive. Therefore the cell reaction is feasible.
(ii) Determine the standard emf of the cell and standard free
energy change of the cell reaction.
Ans. Zn, Zn2+ || Ni2+, Ni. The standard reduction potentials of Zn2+, Zn and
Ni2+, Ni half cells are – 0.76 V and – 0.25 V respectively.
Eocell =EoR – EoL = – 0.25 – (– 0.76)
= + 0.51 V Eocell is + ve. Therefore ∆Go = – ve.
Therefore ∆Go = – n FEocell
n = 2 electrons
Therefore ∆Go = –2 × 96495 × 0.51 = –97460 Joules = – 97.46 kJ.

SECTION B (Answer any two questions)

Question 5 (a). Describe the extraction of Cu from its ore under the following heads:
(i) concentration (ii) Roasting (iii) Reduction (iv) Refining of crude metal. [3]

(Ans). The main ores of copper are copper pyrites (CuFeS2) and copper glance (Cu2S).
The various steps usually involved are given below:
Concentration: Concentration is done by froth-floatation. The finely powdered ore is
mixed with water and pine oil in large tank. The ore particles are wetted by the oil,
whereas the gangue particles are wetted by water. Air is blown through the mixture. As a
result oil froth containing ore particles is formed which floats on the top of the water and
can be skimmed off easily.
Roasting: The concentrated ore is roasted. Roasting is done in reverberatory furnace.
Roasting
2CuFeS2 + O2 Cu2S + 2FeS + SO2
Cu2S and FeS are partially oxidized.
2Cu2S + 3O2 ⎯⎯→ 2Cu2O + 2SO2
2FeS. + 3O2 ⎯⎯→ 2FeO + 2SO2
Reduction : Takes place in Bassemer converter. It can be tiled in any position. It has a
basic lining inside.
The little FeS present in matte is completely oxidized to FeO and then changed into slag
with reaction of silica. Cuprous sulphide reacts with Cu2O to form blister copper.
Cu2S + 2Cu2O ⎯⎯→ 6Cu + SO
Refining of copper : The impure copper metal is purified by the process of electrolytic
8
refining to get pure copper metal.

The impure metal is made the anode and a strip of pure copper cathode. These are
immersed in a copper sulphide solution with a little sulphuric acid added to it. On passing
an electric current the anode begins to dissolve pure copper gets deposited on the cathode.

The impurities either dissolves in the solution or deposited below the anode as anode
mud.

At anode : Cu (Copper) Cu2+ (copper ion)

At cathode : Cu2+ (Copper ion) Cu (Copper atom) deposits on

cathode

Thus pure copper is obtained at the cathode.

(b) Write balanced equations for the following: (i) NaCl is heated with sulphuric acid in
the presence of MnO2. (ii) Chlorine gas is passed into a solution of NaI in water. [2]

Ans. (i)

(ii)

9
Question 6

(a) Write the IUPAC names of the following coordination compounds:

(i) [Co(NH3)6]Cl3 (ii) [Co(NH3)5Cl]Cl2 (iii) K3[Fe(CN)6] (iv) K3[Fe(C2O4)3]
(v) K2[PdCl4] (vi) [Pt(NH3)2Cl(NH2CH3)]Cl [2]

Ans. (i) Hexaamminecobalt(III) chloride

(ii) Pentaamminechloridocobalt(III) chloride
(iii) Potassium hexacyanoferrate(III)
(iv) Potassium trioxalatoferrate(III)
(v) Potassium tetrachloridopalladate(II)
(vi) Diamminechlorido(methylamine)platinum(II) chloride

(b) Using IUPAC norms write the formulas for the following:
(i) Tetrahydroxozincate(II)
(ii) Potassium tetrachloridopalladate(II)
(iii) Diamminedichloridoplatinum(II)
(iv) Potassium tetracyanonickelate(II)
(v) Pentaamminenitrito-O-cobalt(III)
(vi) Hexaamminecobalt(III) sulphate
(vii) Potassium tri(oxalato)chromate(III)
(viii) Hexaammineplatinum(IV)
(ix) Tetrabromidocuprate(II)
(x) Pentaamminenitrito-N-cobalt(III) [1]

Ans. (i) [Zn(OH]2− (ii) K2[PdCl4] (iii) [Pt(NH3)2Cl2] (iv) K2[Ni(CN)4]

(v) [Co(ONO)(NH3)5]2 (vi) [Co(NH3)6]2 (SO4)3 (vii) K3[Cr(C2O4)3](viii) [Pt(NH3)6]4+
(ix) [Cu(Br)4]2− (x) [Co[NO2)(NH3)5]2+

(c) Draw the structures of optical isomers of: (i) [Cr(C2O4)3]3− (ii) [PtCl2(en)2]2+
(iii) [Cr(NH3)2Cl2(en)]+ [1]
Ans. (i) [Cr(C2O4)3]3−

10
(ii) [PtCl2(en)2]2+

(iii) [Cr(NH3)2Cl2(en)]+

(d) Explain the bonding in coordination compounds in terms of Werner’s postulates. [1]
11
Ans Werner’s postulates explain the bonding in coordination compounds as follows:
(i) A metal exhibits two types of valencies namely, primary and secondary valencies.
Primary valencies are satisfied by negative ions while secondary valencies are satisfied
by both negative and neutral ions.

(In modern terminology, the primary valency corresponds to the oxidation number of the
metal ion, whereas the secondary valency refers to the coordination number of the metal
ion.
(ii) A metal ion has a definite number of secondary valencies around the central atom.
Also, these valencies project in a specific direction in the space assigned to the definite
geometry of the coordination compound.
(iii) Primary valencies are usually ionizable, while secondary valencies are non-ionizable.

Question 7
(a) Describe the preparation of potassium permanganate from pyrolusite. How does the
acidified permanganate solution react with (i) iron(II) ions (ii) SO2 and (iii) oxalic acid?
Write the ionic equations for the reactions. [3]
Ans.Potassium permanganate can be prepared from pyrolusite (MnO2). The ore is fused
with KOH in the presence of either atmospheric oxygen or an oxidising agent, such as
KNO3 or KClO4, to give K2MnO4.
heat
2MnO2 + 4KOH ⎯⎯⎯→ 2K2MnO4 + 2H2O
(green)
The green mass can be extracted with water and then oxidized either electrolytically or by
passing chlorine/ozone into the solution.
Electrolytic oxidation
K2MnO4 ↔ 2K+ + MnO2
H2O ↔ H+ + OH-

At anode, manganate ions are oxidized to permanganate ions.

MnO2 ↔ MnO4- + 4e-
Green Purple

Oxidation by chlorine
2K2MnO4 + Cl2 → 2KMnO4 + 2KCl
2MnO42- + Cl2 → 2MnO4- + 2Cl-

Oxidation by ozone

12
2K2MnO4 + O3 + H2O → 2KMnO4 + 2KOH + O2

2MnO42- + O3 + H2O → 2MnO4- + 2OH- + O2

(i) Acidified KMnO4 solution oxidizes Fe (II) ions to Fe (III) ions i.e., ferrous ions to
ferric ions.

(ii) Acidified potassium permanganate oxidizes SO2 to sulphuric acid.

(iii) Acidified potassium permanganate oxidizes oxalic acid to carbon dioxide.

(b) Why is H2O a liquid and H2S a gas? [2]

Ans. H2O has oxygen as the central atom. Oxygen has smaller size and higher
electronegativity as compared to sulphur. Therefore, there is extensive hydrogen bonding
in H2O, which is absent in H2S. Molecules of H2S are held together only by weak van der
Waal’s forces of attraction.
Hence, H2O exists as a liquid while H2S as a solid.
SECTION C (Answer any two questions)
Question 8
(a) How will you convert?
(i) Benzene into aniline. [2]

13
Ans.

(ii) Ethanal into But-2-enal [2]

Ans. On treatment with dilute alkali, ethanal gives 3-hydroxybutanal which on heating
produces but-2-enal.

(iii) Benzaldehyde to Benzophenone. [2]

Ans.

(b) An aromatic compound ‘A’ on treatment with aqueous ammonia and heating forms
14
compound ‘B’ which on heating with Br2 and KOH forms a compound ‘C’of molecular
formula C6H7N. Write the structures and IUPAC names of compounds A, B and C. [3]

Ans. It is given that compound ‘C’ having the molecular formula, C6H7N is formed by
heating compound ‘B’ with Br2 and KOH. This is a Hoffmann bromamide degradation
reaction. Therefore, compound ‘B’ is an amide and compound ‘C’ is an amine. The only
amine having the molecular formula, C6H7N is aniline, (C6H5NH2).

Therefore, compound ‘B’ (from which ’C’ is formed) must be benzamide,

(C6H5CONH2).

Further, benzamide is formed by heating compound ‘A’ with aqueous ammonia.

Therefore, compound ‘A’ must be benzoic acid.

The given reactions can be explained with the help of the following equations:

15
(c) Write chemical reaction of aniline with benzoyl chloride and write the name of the
product obtained. [1]
Ans.

Question 9
(a) Give the equations of reactions for the preparation of phenol from cumene. [2]
Ans. To prepare phenol, cumene is first oxidized in the presence of air of cumene hydro-
peroxide.

16
Then, cumene hydroxide is treated with dilute acid to prepare phenol and acetone as by-
products.

(b) Predict the products of the following reactions: [2]

(i)

(ii)

OC2H5
+ HBr

17
(iii)

OC2H5
Conc.H2SO4
Conc.HNO3

(iv)

HI
(CH3)3C-OC2H5

Ans. (i)

(ii)

18
(iii)

(iv)

(c) Describe a method for the identification of primary, secondary and tertiary amines.
Also write chemical equations of the reactions involved. [3]
Ans. Primary, secondary and tertiary amines can be identified and distinguished by
Hinsberg’s test. In this test, the amines are allowed to react with Hinsberg’s reagent,
benzenesulphonyl chloride (C6H5SO2Cl). The three types of amines react differently with
Hinsberg’s reagent. Therefore, they can be easily identified using Hinsberg’s reagent.
Primary amines react with benzenesulphonyl chloride to form N-alkylbenzenesulphonyl
amide which is soluble in alkali.

Due to the presence of a strong electron-withdrawing sulphonyl group in the

sulphonamide, the H−atom attached to nitrogen can be easily released as proton. So, it is
acidic and dissolves in alkali.
Secondary amines react with Hinsberg’s reagent to give a sulphonamide which is
insoluble in alkali.

19
There is no H−atom attached to the N-atom in the sulphonamide. Therefore, it is not
acidic and insoluble in alkali.
On the other hand, tertiary amines do not react with Hinsberg’s reagent at all.

(d) Give the structures of A, B and C in the following reactions: [3]

(i)
NaCN OH- NaOH,Br2
CH3CH2I A B C
partial hydrolysis

(ii)
CuCN H2O/H+ NH3
C6H5N2Cl A B C
Δ
(iii)
KCN LiAlH4 HNO2
CH3CH2Br A B C
0oC

(iv)
Fe/HCl NaNO2 + HCl H2O/H+
C6H5NO2 A B C
273K Δ
(v)
NH3 NaOBr NaNO2/HCl
CH3COOH A B C
Δ

20
(vi)
Fe/HCl HNO2 C6H5OH
C6H5NO2 A B C
273K
Ans. (i)

O
NaCN OH- ||
CH3CH2I CH3CH2CN CH3 - CH2 - C - NH2
ethyl iodide propanenitrile partial hydrolysis propanamide
(A) (B)

NaOH + Br2

CH3 - CH 2 - NH2
ethanamine
(C)

(ii)

21
(iii)

(iv)

(v)

22
(vi)

Fe/HCl HNO2
C6H5NO2 C6H5NH2 C6H5-N2+Cl-
273K Benzenediazonium chloride (B)
Aniline (A)
C6H5OH

N=N

p-Hydroxyazobenzen (C)

Question 10
(a) How will you convert ? [3]
1) acetaldehyde to formaldehyde
2) benzene to phenol
3) phenol to benzoic acid.

23
(b) Classify the following as addition and condensation polymers: Terylene, Bakelite,
Polyvinyl chloride, Polythene. [2]
Ans. Addition polymers: Polyvinyl chloride, polythene
Condensation polymers: Terylene, bakelite
(c) An organic compound (A) (molecular formula C8H16O2) was hydrolysed with dilute
sulphuric acid to give a carboxylic acid (B) and an alcohol (C). Oxidation of (C) with
chromic acid produced (B). (C) on dehydration gives but-1-ene.Write equations for the
reactions involved. [5]
Ans. An organic compound A with molecular formula C8H16O2 gives a carboxylic acid
(B) and an alcohol (C) on hydrolysis with dilute sulphuric acid. Thus, compound A must
be an ester. Further, alcohol C gives acid B on oxidation with chromic acid. Thus, B and
C must contain equal number of carbon atoms.
Since compound A contains a total of 8 carbon atoms, each of B and C contain 4 carbon
atoms.Again, on dehydration, alcohol C gives but-1-ene. Therefore, C is of straight chain
and hence, it is butan-1-ol.
On oxidation, Butan-1-ol gives butanoic acid. Hence, acid B is butanoic acid.
Hence, the ester with molecular formula C8H16O2 is butylbutanoate.

24
All the given reactions can be explained by the following equations.

25