XIII – SOLUTIONS CHEM PAPER -1 REVIEW TEST-3

Select the correct alternative. (Only one is correct) [27 × 3 = 81]

There is NEGATIVE marking. 1 mark will be deducted for each wrong answer.

Q.25 Which of the following is incorrect statement

(A) I3– is linear in shape and consist 22 valence electrons
(B) HNCO and N3– is linear in shape
(C) hydroxyl amine is more nucleophilic than NH3
(D*) AlN is more ionic than MgO
[Sol: (D) AlN is more ionic than MgO becuase Al3+ has more polarising power than mg2+ but N3– and O2–
polarisation is nearly same.]

Q.26 For the following reaction

CH3–CH2 – Cl + NaOH  CH3–CH2–OH+NaCl
If the reagent is NaOH the best solvent is
(A) water (B*) C2H5OH + H2O (C) C2H5OH (D) only NaOH
[Sol: (B) Alkyl halide is soluble in ethanol & NaOH is soluble in water ]

Q.27 Select the correct statement

(A) bond energy of N  N << P  P
(B) bond energy of P – P < N – N
(C*) Ti(H2O)3+3 is a coloured compound in pure state
(D) AgI2– is unstable while AgF2– is stable compound
[Sol: (C) Ti 22 ® 3d2, 4s2
Ti3+ = 3d1 1 unpaired so coloured ]

Q.28 Organic compound (A) reacts with alc. KOH and gives (B), which on treatment with NaOEt isomerizes
to (C). Compound (C), on treatment with OsO4 followed by HIO4 results CH3CH=O only. Select the
incorrect statement. If A is a monohalogen hydrocarbon with molecular weight is 92.5.
(A) (A) gives yellow ppt. with AgNO3
(B) (A) do not give any ppt. with AgNO3 in NH3
(C) (C) gives brown ppt. with AgNO3/NH3
(D*) (A) reacts with NaI/acetone according to first order rate kinetics.
[Sol: (D) CH3–CH2–CH2–CH2–Cl ]

Q.29 If R–isomer have –ve rotation and S-isomer have +ve rotation, select the correct statement about the
mixture of R and S 2–bromobutane, specific rotation of mixture is +18.40 and specific rotation of R–2–
bromobutane is –230 then select the incorrect statement
(A) S–isomer has 23% specific rotation
(B) 80% excess of S over R isomer
(C) R-isomer has composition 10% only
(D*) None of these
[Sol: R - Isomer  –ve rotation
S-Isomer  +ve rotation
specific rotation of mix is = +18.4 (S excess)
specific rotation of R-isomer(pure) = –23
specific rotation of S-isomer(pure) = +23
18.4
optical purity (ee) =  100 = 80%
23
80% S (excess) + 20% (R + S) ]
Q.30 When 2–chlorobutane reacts with NaOH in presence of ethyl alcohol and water, rate kinetics of reaction
follows

(A) (B)

(C) (D*)

[Sol: (D) rate = K1(R – X)1 (nu)1 + K2 (R – X)1 ]


Q.31 H major product is

(A) (B) (C*) (D)

[Sol:

Q.32 Chirapos was developed by professor Kagan & has found useful applications in asymmetric synthesis.
Using fischer projection shown below, which is correct statement about configuration of the chirapose in
terms of R/S notation.

(A) It is 2R, 3R molecule (B) It is 2S, 3R, molecule

(C*) It is 2S, 3S molecule (D) It is 2R, 3S molecule
Q.33 In the following reaction

Product is

(A) (B) (C*) (D)

[Sol:

Q.34 Select the incorrect statement

(A) Al3+ on treatment with aq. Na2S gives Al(OH)3
(B) Cr3+ on treatment with aq. Na2S gives Cr(OH)3
(C) Cr(OH)3 dissolved in basic solution of bromine water
(D*) When mixture of AgCl, Hg2Cl2 is treated with NH3 and resultant is filtered, black residue consist
HgNH2Cl, Hg, only

Q.35 For the reactions

I NaOAc
 
AcOH

II NaOAc
 
AcOH

Select the correct statement

(A*) rate of Ist reaction is 1011 times faster than trans IInd
(B) rate of IInd reaction is 1011 times faster than trans Ist
(C) rate of Ist reaction and IInd reaction are equal
(D) reaction not possible
[Sol: anchimeric assistance through  bond. ]

Q.36 The equilibrium constant for the ionization of R–NH2(aq) in water as

R–NH2(g) + H2O(l)  R–NH2(aq) R–NH3+(aq) + OH–(aq)
is 8 × 10–6 at 25°C. Find the pH of a solution at equilibrium with pressure of R–NH2(g) is 0.5 atm.
Assume Henry's Law, at equilibrium PA = K[A]; where K =1.[Take log 2.82 = 0.45]
(A)  12.3 (B*)  11.3 (C)  11.45 (D) None
x2
[Sol. 8× 10–6
=
0 .5
4 × 10 = x2
–6

x = 2 × 10–3
 pOH = 2.7
So, pH = 11.3 ]

Q.37 Which statement(s) is/are true about the relation between the following compounds?

(a) (b) (c)

(I) a and b are tautomers (II) b and c are resonating structures

(III) a and c are resonating structures (IV) a and c are tautomers
(A*) I & III (B) II & IV (C) I, II & III (D) I & IV

Q.38 Arrange the following carbocations in the increasing order of their stability.

(I) (II) (III)

(A*) I > II > III (B) I > II = III (C) I > III > II (D) III > I > II
[Sol. (I) Two benzenoid RS & Two H
(II) Two benzenoid RS & but zero H
(III) Only one benzenoid RS zero H ]

Q.39 Which statement about the following equilibrium is/are true?

 
Ph3C–H + Me O K

Ph3C K  + MeOH
(I) The reaction favours the product formation.
(II) Ph3CK is the dominant anionic species in this reaction.
(III) Methanol is the weaker acid in this reaction.
(IV) The reaction favours the reactant formation.
(A) I & II (B) I, II & III (C*) IV only (D) III & IV
[Sol. Reaction moves towards weaker acid & base ]
Q.40 Which one of following carbonyl compound when treated with dilute acid forms the most stable
carbocation?
O O
|| ||
(A) CH 3  C  CH 3 (B) (C*) (D) C6 H 5  C  C 6 H 5

[Sol. C will form aromatic cation by attack of Hon carbonyl oxygen.]

Q.41 Correct order of heat of combustion is:

(p) 1,3-Pentadiene (q) 1,3-Butadiene
(r) 2,3-Dimethyl-1, 3-butadiene (s) Propadiene
(A) s > q > p > r (B) s > r > q > p (C*) r > p > q > s (D) s > r > p > q
[Sol. More the no. of C & H in the compound more will be heat of combustion]

Q.42 Write correct order of reactivity of following halogen derivatives.

(I) (II) CH2=CH–Cl (III) Et3C–Cl (IV) PhCH2Cl (V) Ph3C–Cl

(A*) I > V > IV > III > II (B) V > IV > I > III > II
(C) V > I > IV > III> II (D) I > V > III > IV > II
[Sol. Reactivity of R–X increases with decrease in BD.E. of RX & increase in stability of carbocation formed.]

Q.43 Correct order of nucleophilicity of following anions in polar protic solvent is:

(A*) CH3 >


NH 2- > OH  > F  (B) CH3 <

NH 2- < OH  < F 

(C) CH3 =

NH 2- = OH  = F    -
(D) CH3 > F > OH > NH 2


[Sol. Nucleophilicity decreases with increase in electronegativity of donor atom.]

Q.44 NO2 is involved in the formation of smog and acid rain. A reaction that is important in the formation of
NO2 is
O3(g) + NO(g) O2(g) + NO2(g) K = 6 × 1034
If the air over a section of Pooja Towers contained 1.0 × 10 –6M O3, 1.0 × 10–5M NO, 2.5 × 10–4M
NO2 and 8.2 × 10–3M O2, what can we conclude
(A) there will be a tendency to form more NO and O3
(B*) there will be a tendency to form more NO2 and O2
(C) There will be a tendency to form more NO2 and O3
(D) There will be no tendency for change because the reaction is at equilibrium
O2  NO2  8.2 103  2.5 104
[Sol: Q= O3  NO  = = 2.05 × 105
1.0 106 1.0 105
As Q < K
Thus forward reaction will take place ]
Q.45 The equilibrium SO2Cl2(g) SO2(g) + Cl2(g) is attained at 250C in a closed container and Helium
is introduced. Which of the following statement is correct
(1) The concentrations of SO2, Cl2 and SO2Cl2 change
(2) More chlorine is formed
(3) Concentration of SO2 is reduced
(4) More SO2Cl2 is formed
(A) 1, 2, 3 (B) 2, 3, 4 (C) 3, 4 (D*) none of these
[Sol: At constant volume addition of inert gas Helium does not effect the equilibrium]

Q.46 In the system LaCl3(s) + H2O(g) + heat LaClO(s) + 2HCl (g) equilibrium is established. More
water vapour is added to re-establish the equilibrium. The pressure of water vapour is doubled. The
factor by which pressure of HCl is changed is
(A) 2 (B*) 2 (C) 3 (D) none of these
[Sol: LaCl3(s) + H2O(g) + heat LaClO(s) + 2HCl (g)
HCl 2
K= After doubling the concentration of H2O [H2O]new = x
H 2O 
[H2O] = x And at equation, [HCl]new = 2 · [HCl]

Q.47 Which of the following compound has pyramidal geometry?

(A) B(CH3)3 (B) (CH3)3C (C*) (CH3)3N (D) BF3

Q.48 20 ml of 0.2 M – NaOH and 40 ml 0.1 M – H2SO4 are mixed together in a flask & volume made up to
250 ml. The pH of the resultant solution is
(A) 5 (B) 6 (C) 8 (D*) none of these