XIII –SOLUTIONS PAPER II CHEM REVIEW TEST-3

PART-A
Select the correct alternative. (More than one is/are correct) [3 × 6 = 18]
There is NEGATIVE marking. 1 mark will be deducted for each wrong answer.

Q.4 Which of the reactions can be predicted by the colour of the product
(A*) Mn2+ + NaBiO3 + HNO3  HMnO4 + Bi(NO3)3 + NaNO3 + H2O
(B*) Fe3+ + [Fe(CN)6]3–  Fe[Fe(CN)6]
(C*) PO43– + (NH4)2MoO4 + HNO3  (NH4)3PMo12O40 + NH4NO3
(D) (NH4)2S2  (NH4)2S + (NH4)2S3
[Sol: (NH4)2S2 and (NH4)2S3 both are yellow coloured. ]

Q.5 Select the correct statement

(A*) on treatment with NaCN retains its configuration

(B*) on reaction with NaN3 changes its configuration

(C*) reacts faster than on treatment with H2O according to first

order rate kinetics

(D*) CH2 = CH–CH2–CH2–Br on treament with water undergoes solvolysis with very high rate and
yields CH2=CH–CH2–CH2–OH
[Sol: (A) As the reaction is taking place at non stereocentre
(B) C–Br bond being cleaved
(C) stability of carbocation is reponsible for such an observation
(D) Anchimeric assistance of p-bond

C N replaced Br only therefore retention of configuration
 answer is ABCD ]

Q.6 Select the correct statement(s)

(A) 30 butyl alcohol on treament with brosyl chloride followed by mixture (equimolar) of NH4Cl, NH4Br,
NH4I, results more iodide product than chloride
(B*) on treament with Tosyl chloride followed by equimolar mixture of NH4Cl, NH4Br,,

NH4I results more Iodide product than Bromide.

 (C*) Organic compound on reaction with aq. KOH gives EtOH by

second order rate kinetics.

(D) None of these
[Sol: In B after retention with Tosyl chloride poor leaving group convert into good leaving.
Therefore answer is BC ]

PART-B
MATCH THE COLUMN [3 × 8 = 24]
INSTRUCTIONS:
Column-I and column-II contains four entries each. Entries of column-I are to be matched with some
entries of column-II. One or more than one entries of column-I may have the matching with the same entries
of column-II and one entry of column-I may have one or more than one matching with entries of column-II.
Q.4 Match the column:
Column I Column II

(A) (P) Conformation of maximum torsional strain

(B) (Q) Conformation with strong intramolecular hydrogen bond

(C) (R) Highest boiling point

(D) (S) Conformation of minimum Vander Waal strain

[Ans. (A) R, (B) Q, (C) P, (D) S ]

[Sol: (A) Trans isomer as both are axial
 high Boiling Point (R)
(B) Intramolecular H–bonding (Q)
(C) Exchange interaction (P)
(D) ANti conformer (S) ]
Q.5 Reaction Type
(A) Substitution nucleophilic bi molecular (P) 10 > 20 > 30 halides
(B) Elimination unimolecular (Q) 30 > 20 > 10 halides
(C) Substitution nucleophilic unimolecular (R) Racemization of configuration
(D) Elimination bi molecular (S) Inversion of configuration
[Ans. (A) PS (B) Q (C) Q,R (D) Q]
[Sol: (A) Bimolecular (PS)
(P) Because of min. steric factors
(Q) Back face attack
(B) stability of carbocation (planar) (Q)
(C) stability of carboation (planar) (Q, R)
(D) Less hindrance on hydrogens (Q) ]

Q.6 Reaction Intermediate Name of the Reaction

(A) Carbocation (P) –elimination
(B) Cl2 (Q) E1 & S N 1

(C) (R) Reimmer Tiemann reaction

(D) (S) Hoffmann Bromoamide degradation

[Ans: (A) Q (B) PR (C) PS (D) P ]

[Sol: (A) Carbocation (Q)


(B) CHCl3 OH 
 e lim inates
 C Cl3    :CCl2

+ CHCl3 + KOH  proceeds by :CCl2 (PR)

(C) (PS)

(D) formed by (P)

 PART-C
SUBJECTIVE: [5 × 10 = 50]
Q.6 The specific rotation for a pure enantiomer is known to be –390g–1ml–1dm–1. A sample containing both
enantiomers is found to have a an observed rotation of –0.620 in a one dm tube at a concentration of 3.5
g/100ml. What is the optical purity of the sample.
[Sol: For this sample, the apparent specific rotation is
0.62
[] = 
0.035 1
[] = –17.7 g–1mL–1dm–1
If the fraction of (–). Enantiomers is x, then (1 – x) gives the fraction of the (+) enantiomer. For any
mixture of the two specific rotation will be given by
x(–390) + (1 – x) (+390C) = []apparent
For this mixture
–78 x = –56.7
x = 0.73
 % of (–) enantiomer = 73
and ........(+) enantiomer = 27 ]

A
C C  Ph
   
Q.7 EtO
 K
  Reaction intermediate Ph  B EtO
 K
  C  D
HBr

Write the formula weight of D.



EtO
[Sol: Ph – CHCl2 

K

347 Ans. ]
Q.8 When 1 mole of A(g) is introduced in a closed rigid 1 litre vessel maintained at constant temperature the
following equilibria are established.
A (g) B(g) + C(g) : KC
1

C (g) D(g) + B(g) : KC

2

KC [C]eq 1
2
The pressure at equilibrium is twice the initial pressure. Calculate the value of if =
KC [B]eq 5
1

[Ans. 4]
[Sol. A (g) B(g) + C(g) : KC
1

1–x (x+y) (x–y)

C (g) D(g) + B(g) : KC
2

(x–y) y (y+x)
ntotal = (1 – x) + (x + y)(x – y) + y
2 =1+x+y
 x+y =1 ...(1)
xy 1
Also, =  5x – 5y = x + y
xy 5
 4x = 6y  x = 1.5 y ...(2)
From eq. (1) & (2)
1.5y + y = 1  y = 0.4
So, x = 0.6
( x  y)( x  y) 1 0.2 1
Now, KC = = =
1 (1  x ) 0.4 2
y( x  y) 0.4 1
KC = = =2
2 ( x  y) 0.2
KC
2
Thus, =4 ]
KC
1

Q.9 500 ml of 0.2 M aqueous solution of acetic acid is mixed with 500 ml of 0.2 M HCl at 250C
(i) Calculate the pH of the resulting solution. (not to be reported)
(ii) If 6 gm of NaOH is added to the above solution, determine the final pH. (not to be reported)
[Assume there is no change in volume on mixing, Given pKa of CH3COOH = 4.74]
Report your answer as a sum of pH in 1st case and pH in 2nd cases.
[Sol: (i) m moles of CH3COOH = 500 × 0.2 = 100
m moles of HCl = 500 × 0.2 = 100
100
so, in solution [CH3COOH]0 = = 0.1 M
1000
100
[HCl]0 = = 0.1 M
1000
In presence of HCl (Strong electrolyte), ionisation of CH3COOH (weak electrolyte) is negligible
 HCl  H+ + Cl–
0.1 0.1
  [H+]solution = [H+]from HCl + H

  from CH 3COOH

[H+]solution = [H+]from HCl = 0.1

pH = –log [H+] = 1
6
(ii) moles of NaOH added = = 0.15
40
being strong electron H+ frm HCl reacts first with NaOH
so moles of NaOH reacts with HCl = 0.1
& moles of NaOH reacts with CH3COOH = 0.15 – 0.1 = 0.05
CH3COOH + OH–  CH3COO– + H2O
t=0 0.1 0.05
eqn. 0.05 – 0.05

 pH = pKa + log
CH COO 
3


CH 3COOH 
 0.05 
pH = 4.74 + log   = 4.74
 0.05 
Therefore answer to be reported = 1 + 4.74 = 5.74 ]

Q.10 The equilibrium constant Kp for the reaction

N2O4 (g) 2NO2(g) is 4.5 at temperature T..
What would be the average molar mass (in gm/mol) of an equilibrium mixture of N2O4 & NO2 formed
by the dissociation of pure N2O4 at a total pressure of 2 atm at temperature T.
[Ans. 57.5]
[Sol. Let initial mole of N2O4 (g) is one
N2O4 (g) 2NO2 (g)
Initial moles 1 0
At equilibrium 1– 2

Total no. of moles at equilibrium = 1 + 

1  2
Now, PN = P; PNO = P
2O 4 1  2 (1  )
2
PNO 4 2
Hence Kp = 2
= P
PN (1 –  2 )
2O 4

4 2
 4.5 = 2
(1 –  2 )
4.5 – 4.5 2 = 82 ; 12.5 2 = 4.5
2 = 9/25 ;  = 3/5 = 0.6
1  0 .4
Mole fraction of N2O4: x N 2O 4 = = = 0.25
1  1 .6
 x NO = 0.75
2

Average molar mass of mixture = 0.25 × 92 + 0.25 × 46 = 57.5 ]