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Dish A 500 Prob Chem
Dish A 500 Prob Chem
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Preface
We are glad to present our latest book. During our teaching experience, we realized that
there is a gap of very few days between JEE Main and JEE Advanced. So there is very little
time for students to revise/ go through all the concepts in the various subjects. The students
can now put their worries to REST. We have come up with a unique book which provides
Chapter-wise BLOCKBUSTER PROBLEMS covering all the important concepts which a
student should revise before appearing for JEE Advanced Exam. Questions in the books are
carefully designed so as to be exactly similar to the ones that come in JEE Advanced Exam.
Salient features of this book:
The book has been divided into a total of 21 Chapters.
Each Chapter contains one or more than one option correct, Integer type, Matching Type,
Passage-based, and Numeric Value Type questions.
The book is 100% Solved and it contains solutions to each and every question.
The sole aim of this book is to revise all important concepts in a short span of time just by
solving questions. Problems have been designed keeping in mind the examiner's point of
view and current examination patterns.
We hope that the present book will be useful to JEE aspirants. There is no better remuneration
that the satisfaction of the students and teachers. We strongly believe that a student, who
masters all the questions provided in this book, will improve his score in JEE Advanced by
10-15%. We also expect some questions (exact/ similar) from this book to appear in the
upcoming JEE Advanced Exam.
We would like to thank Disha Publication for providing us this opportunity. We would
also like to thank Preetima Bajpai of Disha Publication who has provided her continuous
support in bringing this book to its present shape.
At last, constructive criticism and valuable suggestions are most welcome from the readers
to make the book more useful in the upcoming editions.
Authors
Vaibhav Trivedi
Yogesh Pathak
Contents
1. Some Basic Concepts of Chemistry
6. Equilibrium 41-48
https://telegram.me/Unacademyplusdiscounts_link
https://telegram.me/Unacademyplusdiscounts_link
https://telegram.me/Unacademyplusdiscounts_link
(a) 2'.. must be less than 1.33 (b) 2'.. must be greater than 1. 33
X X
(c) 2'.. must be greater than 2.67 (d) 2'.. must lie between 1. 33 and 2 .67
X X
7. 40gH2
40gmolecule 0 2
44.8 lit N 2 at STP
What amount of He should be introduced in this container so that resulting mixture should have
4.2154 x 1025 gaseous particles.
(a) 32 g (b) 36 g (c) 8 g atom (d) 9 g atom
8. A chloride mixture is prepared by grinding together pure BaC12 .2H2 O, KCl and NaCl. What is the
smallest and largest volume of 0.15 M AgNO3 solution that may be used for complete precipitation of
chloride ion from 0.3g sample of the mixture which may conatin any one or all of the constituents
(a) Smallest volume is 16.38 ml (b) Largest volume is 34.18 ml
(c) Largest volume is 16.38 ml (d) Smallest volume is 8.18 ml
9. A quantity of 0.22 g of a gas occupies a volume of 112 ml at pressure ofl atm and temperature of 273
K. The gas may be
(a) Nitrogen dioxide (b) Nitrous oxide (c) Carbon dioxide (d) Propane
10. Red ink is composed of eosin (molar mass 692). If 'YOGESH PATHAK' is written by red ink, it
weighs 1.73 x 10-10 g and 'VAIBHAV TRIVEDI' is written by graphite pencil, it weighs 3 x 10-12 g.
Select correct statements.
(a) Graphite particles are more than eosin particles.
(b) Eosin particles are greater than graphite particles.
(c) Both graphite and eosin have same number of particles.
(d) Mol percentage of 'Br ' in eosin is 10.8.
Br Br
Eosin
15. Find the mass of Cu(NO 3)2.3H 2O produced by dissolving 10 g of copper in nitric acid and then
evaporating the solution?
16. Calculate molality of 1 litre solution of 93% H 2SO4 (WN). The density of solution is 1.84 g mL-l _
( I ) Integer Answer
17.
18.
105 mol of pure water is saturated w ith NH3 gas producing a solution of density 0.9 g/ml. If the
(A) N2
Match the Column-I with Column-II :
Column-I
(p) 40% carbon by mass
Column-II
•
(B) co (q) Empirical formula CH 2O
(C) C6H1 2O6 (r) Vapour density = 14
(D) CH 3COOH (s) 14NA (NA = 6.023 x 1023) electrons in a mole
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4 CHEMISTRY
Passage-II
H 20 2 is used to produce 0 2 which can be used for the oxidation of other substances. The strength of
H 2 0 2 is expressed in several ways like M, N, % (WN) and volume strength. If a bottle of H 2 0 2 is
labelled as "20 volume", it means that 1 litre ofH2 0 2 sample will release 20 litre of 0 2 at S.T.P.
1
H 2 0 2 (aq) ➔ H 2 0(l)+-0 2 (g)
2
25. What is the strength of 20 volume H 2 0 2 ?
(a) 60. 71 g/lit (b) 30.5 g/lit (c) 3.05 g/lit (d) 6.071 g/lit
26. What is the % strength (WN) of 11.2 volume H 2 0 2 ?
(a) 1.7 (b) 34 (c) 3.4 (d) 17
RESPONSE SHEET
1. ~®@@ 2. ~®@@ 3. ~@@@
4. ~®@@ 5. ~®@@ 6. ~@@@
7. ~®@@ 8. ~®@@ 9. ~@@@
10. ~®@@ 11. 12.
19. 20.
ANSWER KEYS
1. a 2. a 3. d 4. a 5. a 6. a 7. a, C
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6 CHEMISTRY
6. (a) Suppose moles ofN2, NO2 and N 2O 4 are x, 9. (b, c, d) Molar mass of gas
y and z respectively. 0.22
= -- X 22400 = 44
x+y+z =l ... (1) 112
28x + 46y + 92z = 55 .4 ... (2) C3H 8, CO2 and N 2O have molar masses 44 g.
(x+y+2z) x 39.6=55.4 ... (3) 3Xl0-12
On solving, 10. (c, d) Graphite particles = - -- -N A
12
X = 0.5 ,y = 0.1 , Z = 0.4 = 0.25 x 10-12 NA
7. (a, c) 4.2154 x 1023 particles l.73 X l0- 10
Eosin particles = NA
= 4.2154 x l025 = 70 mole 692
6.O22Xl0 23 = 0.25 x 10- 12 NA
Moles in the container Hence, both have same particles. Molecular
formula of eosin is C 20H 6Br4Na2 Os-
= 40 + 40 + 44.8 = 62
2 22.4 In one mol of eosin, 4 mol of 'Br' are present.
8. (a, b) Smallest volume of AgNO3 would be 11. (3.04) Balance the reaction in terms of 'n' as
required when the entire mass is due to highest 4nXeF6 +-fCH 2 -CH 2 h ➔ -fCF2 -CF2t-n
molecular weight constituent. Hence, for
+ 4nHF + 4nXeF4
smallest volume, the whole mass should be of
XeF2 + 2F2 ➔ XeF6
BaCI2 .2H 2 O
Formula weight of one unit of fluorivated
m mol ofBaC12 .2H2 O
polymer = 100,
0.3
=- x l000 = 1.229m mol For 1 kg, n = 10
244
40 moles ofXeF2 would be required and for this
m mol of AgNO 3 required
80.00 moles ofF2 would be consumed.
=2 X 1.229 = 2.458
Hence, mass ofF2 = 80 x 38 = 3040 = 3.04 kg.
Volume of AgNO3 required
12. (99) Let mass of Fe = x g
2.458
= - - = 16.38 mL (smallest) 0 ~
0.15
Fe +dil. H 2 SO4 ~ FeSO4
Largest volume of AgNO3 would be required 100 ml
when entire mass is due to lowest molecular y moles
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Some Basic Concepts of Chemistry 7
568 5
Moles of P4 O10 = - =2 V = 00 = 166.67 ml
284 3
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8 CHEMISTRY
2 1. A- r, s ; B - r, s; C - p , q, D - p , r 25. (a) 20 volume H 2O 2 m eans 1 lit. H 2O 2 will
22. A- p , r, B - p , q, r, C - p , r, s , D - p , r, s give 20 lit 0 2 at S.T.P.
23. (b) M eq. of (NH4 ) 2C 2O 4 = Meq. of NH 3 2H 2O 2 ~ 2H 2O+O 2
= Meq. ofH 2SO 4 used
2 X 34 g 1 m ol = 22.4 litre at STP
w
_ x l000 = Meq. ofNH 3 = 3.663 22.4 lit 0 2 will be produced by
124 10
2 = 2 x 34 g H2O2 = 68 g HP2
[Meq. ofH 2SO 4 used= (0.05035 x 2 x 50 So, 20 lit 0 2 will be produced by
-11.3 X 0.1 2 14) = 3 .663] 68
= - - x 20 = 60.7 1 g ofH2O 2
:. w(NH )zc 204
4
= 0.2273g 22.4
and as we have initially mentioned that 20 lit
:. Percentage of (NH 4)iC2O 4
0 2 is produced by l litre of H 2O 2 . Hence, in
0.2273
= - ~ x l00 = 47.8% one litre ofH 2O 2 , 6 0. 71 g H2 O 2 is present. So,
0.4773
24. (d) M eq. of N = Meq. of NH 3 strength ofH2 O 2 will be 60.71 g/lit.
w 26. (c) Strength in percentage means how many
or - XlO00 = 3.663
14 gram H 2 O 2 present per 100 ml
or ~ = 0.0513g ·: M = l and m ol wt. ofH 2O 2 = 34
2
0.0513 :. 34 g H 2O 2 present per litre of solution or 3.4
:. Percentage ofN = - -xlO0 = 10.74%
0.4775 g H 2 O 2 present per 100 ml of solution.
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Atomic Structure
7. Let An be the area enclosed by nth orbit in H-atom. The graph log(~:) vs. log n
(a) will pass through origin
(b) will be straight line with slope 4
(c) will be m onotonically increasing non-linear curve
( d) will be rectangular hyperbola
8. Which of the following can be concluded correctly from the solution of Schrodinger equation
(a) For all orbitals, the radial wave function (\I') approaches infinity
(b) The radial probability density (\11 2) for ls orbital is maximum at nucleus
(c) The radial distribution function (4nr2\1'2) for l s orbital is minimum at the nucleus
(d) In plot ofradial wave function (\I'), \I' changes its sign at nodes
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10 ===================== CHEMISTRY
9. If the Aufbau principle is not followed in filling up electrons in the subshells, the block (s, p, d or f)
of which element will change in the periodic table?
(a) K (19) (b) Sc (21) (c) V (23) (d) Sr (38)
10. Which of the following is/are true for the given nuclear reaction?
90 Th22s -----4 g3Bi212
(a) A total of 4 a and 1 ~ particles are emitted per nucleus of Th
(b) 90Th228 is above the band of stability
(c) A total of 5 a and 3 ~ particles are emitted per nucleus of Th
(d) 90Th228 is decaying to 83 Bi212 because later is the most stable isotope
11.
Numeric Value Answer
( I ) Integer Answer
17. An electron in a hydrogen like species is in the excited state (n2). The wavelength corresponding to a
■
transition to second orbit is 48.24 nm. From the same orbit, wavelength corresponding to a transition
to third orbit is 142.6 nm. The value of n2 will be
18. Total number of subshells which can haven + l = 5 are
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Atomic Structure 11
G 3s
lclnl EI
The spin quantum numbers of electron B and E are + ~. For how many pairs of electrons, three of
2
quantum numbers are identical?
20. The value of de-Broglie wavelength of the gas at- 73 °C is 'M ' times that of the de-Broglie wavelength
ofNe at 727 °C. The value ofM is
\ I'-
\J
~
(B) 4s (q)
(C) 2p (r)
(\
v-
(D) 3p (s)
\(\
V V
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12 CHEMISTRY
RESPONSE SHEET
1. (i)@(s)@ 2. (i)@(s)@ 3. (i)@(s)@
4. (i)@(s)@ 5. (i)@(s)@ 6. (i)@(s)@
7. (i)@(s)@ 8. (i)@(s)@ 9. (i)@(s)@
10. (i)@(s)@ 11. 12.
19. 20.
ANSWER KEYS
1. C 2. C 3. b 4. d 5. a 6. a 7. a, b
8. a, b,c, d 9. a, d 10. a, b 11. 1.6 12. 64 13. 7.5 14. 11
\ I I
•' •
_ ___......,,.. .
_... \ ..._
..•,g.,._ _ __ Hints & Solutions : I :
1. 5x 6.626x l0- 34
= -------------
(3 X3.18 Xl0-23 X300 X9.1XI0- 31)l / Z
~
4. (d) Radioactive cobalt is used for the treatment
of hyperthyroidism. A1
=n4, log(AnA )=4logn, ISlope= 41
1
Probability density at r = a 0 \jt2(a0 ) y = mx
5. (a) Prob abT =
1 1ty dens1ty
. at r = 0 \jf 2 (0) 8. (a, b , c, d)
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14 CH EMISTRY
1 2
12. (64) K.E. = - mv = -1 mx
2 2
= ----
⇒ X + n = 7 + 4 = [DJ.
8mrt2 xr2
15. (2 l )No.of sp ectralline
For second Bohr orbit, n = 2
(n2 - n1)(n2 - n1 + 1)
r = r0 n 2 = 4r0 =
2
(2)2 xh 2 4h 2 (8 - 2)(8 - 2 + 1)
= - .:.._:_- - - = =
8mrt2 x(4r0 )2 8rt2 mxl6rJ 2
h2 = 6( 6 + l) = 3 X 7 = 21.
=--- 2
E =he= 12400 = ~ eV
').., 1600 4
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Atomic Structure 15
Case 2: 1
E: n=3 l=l m=+l s=+ -
! 11.3
11
= 4.25 eY
' ' - ' 2
l 11.4 = 5.95 eY
- - - - - - - - - 11 = 3 (Second excited state)
(AB), (CD), (DE), (CE), (AD) pairs have any
three quantum numbers identical.
_l__ (~--nJ1J
142.46 -
R
H
z2
9
... (2) ls 0 0
22. A- p; B - s; C - q; D - r
From ( 1) and (2) after solving n 2 = 5. 23. (a) The electrons being present in pt shell and
18. (3) n l another shell n 1. These are excited to higher level
0 5 not possible n 2 by absorbing 2.7 eV and on de-excitation
1 4 lg (not possible) emits six A and thus excited state n 2 comes to
2 3 2/ (not possible) be 4.
3 2 3d (possible) 6 = Un = I:(n2 - 1), hence n2 = 4
4 1 4p (possible)
RHch RHch -RHch
5 0 5s (possible) E1= - l2 ,En1 = - -
2- ,E4= 2
n1 4
1
19. (5) A: n = 3' l = 0' m = 0 , s = + -2 Since, de-excitation leads to different A having
1 photon energy greater or lesser than 2. 7 eV
B: n = 3' l = 0' m = 0 , s = - -2
and thus absorption of 2.7 eV energy causing
1 excitation to 4th shell and then re-emitting
C: n=3 ' l=l, m=+l
- ' s=+-
2
photons of greater or lesser than 2.7 eV is
1 possible only when n 1 = 2 (the de-excitation
D : n = 3' l = l ' m = 0 , s = + -2
from 4th shell occurs in 1, 2 and 3 shell).
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16 CHEMIST RY
E4 -E2 = 2.7 eV 3 1
25. (a) n = 2 l = l 1· = - or -
E4 -E3 < 2.7 eV ' ' 2 2
E4 -E1 > 2.7 eV 3 1 1 3 3
m =- 2' - 2 ' +2' +2 for j = 2
RHch E
:.En =E2 = - - = - 1 1 1 1
1 22 4 = - - , + - for j = -
hence, n 1 = 2. 2 2 2
26. (c) n = 3
24. (b) E4-E2=2.7eV
1 1 1
l = 0, j = 2' m = -2, +2
E1 E1
- - +- = 2.7 eV, E 1 = -14.4 eV
(4) 2 (2) 2 _ 3 3 1 1 3
l = 2 ' 1 = 2' m = - 2, - 2, +2' +2
Hence, ionisation potential= 14.4 eV.
5 5 3 3
= - ⇒ m=- -
2
- - - -
2' 2' 2 '
1 1
+-2' +-2' +-52
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Periodic Properties
and Chemical
Bonding
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18 ===================== CHEMISTRY
(c) H 20 2 and 0 2F2 have similar structures, hence, the O - 0 bond of the two molecules is identical.
(d) Rotation about O - 0 bond in H20 2 and 0 2F2 is a free rotation.
8. Ionisation energy of an element is :
(a) Equal in magnitude but opposite in sign to the electron gain enthalpy of the cation of the element.
(b) Same as electron affinity of the element.
(c) Energy required to remove one valence electron from an isolated gaseous atom in its groumd
state.
(d) Equal in magnitude but opposite in sign to the electron gain enthalpy of the anion of the element.
9. Which of the following increases the basic character of elements?
(a) Increasing metallic character of element (b) Increasing electronegativity of metal
( c) Decreasing ionisation potential of metal (d) Decreasing effective nuclear charge
10. Species where 0-bond is absent is/are
( I ) Integer Answer
11. Total number of mixed an hydrides among :
0 0 0 0
•
N204, N203, Cl207, Cl206, )lo~ , Jo\
Cl Cl
18. Total number of species having bond order greater than that of co EB .
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Periodic Properties & Chemical Bonding 19
Lewis concept of covalency of an element involved octet rule. Later on it was found that many
•
elements in their compounds, e.g., BeF2 , BF3 etc. have incomplete octet whereas PC15 , SF6 etc. have
expanded octet.
This classical concept also failed in predicting the geometry of molecules. Modern concept of
covalence was proposed in terms of V.B.T. Hybridisation concept along with V.B.T. successfully
explained the geometry of various molecules.
2 1. Which are true statements among the following ?
I. Ie
3
has bent structure
II. pn - dn bonds are present in SO 2
III. XeFf has pentagonal planar shape but PC15 is triangular planar
IV MgSO 3.3H 2 O and MgCO 3.3H2 O are isomorphs
(a) II, III (b) II, III, IV (c) I, II, III (d) I, II, III, IV
22. The bond angles in Nor , NO2 and NOf are respectively :
(a) 180°, 134°, 115° (b) 11 5°, 134°, 180° (c) 134°, 180°, 115° (d) 115°, 180°, 130°.
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20 CHEMISTRY
Passage-II
The platinum-chlorine distance has been found to be 2.32 A in several crystalline compounds. This
value applies to both of the compounds shown :
N H3 NH3
I I
Cl - Pt - Cl Cl - Pt - N H3
I I
NH3 Cl
(A) (B)
RESPONSE SHEET
1. (i)@(s)@ 2. (i)@(s)@ 3. (i)@(s)@
4. (i)@(s)@ 5. (i)@(s)@ 6. (i)@(s)@
7. (i)@(s)@ 8. (i)@(s)@ 9. (i)@(s)@
10. (i)@(s)@ 11. 12.
19. 20.
ANSWER KEYS
1. a 2. d 3. d 4. b 5. b 6. d 7. b, c
8. a,c 9. a, c, d 10. a, d 11. 3 12. 7 13. 3 14. 4
.. '. .._
\ I I \ I I
_
Hints & Solutions :
.I .:
• ,c;i..__ __
----- ·
1. (a) (I) contains P ➔ 0 bond while in (II) back 6. (d)
bonding takes places. 1
7. (b, c) Electronegativity oc - - - -
Bond length
£1 £2
F- 0 - 0 - F H- 0 - 0 - H
8. (a, c)
9. (a, c, d)
10. (a, d)
N
F it cr cr it
Ill C= C , F- F , 0 = 0 , 8 - B
2. (d)O = C< 08° S- F 1t 1t
~ F
F
MF 0 0
F F 11. (3) N 20 4 , Cl2 0 6 , )lO~
1so( I ::::::::- o
0
F I F
g I :::::::::a ) I~ 0° approx.
I F II F
F 0
3. (d)
4. (b)
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22 CHEMISTRY
19. A-r;B-p;C -q,s; D-p
oxidation state of lanthanoid is + 3. Effective 21. (c) IV is wrong because for isomorphs both the
atomic number in Mn(CO)5 is 35 so it will anions must have same geometry.
favour reduction.
16. (1) Except Cu rest all are bigger than 'Zn '. are 180°, 134° and ll5° respectively. Nof
and NOf undergoes sp and sp2 hybridisation
F
respectively.
l ✓,::O
17. (2)@Xe~prc-drc bonds 23. (b)
I
~o because Xe is 24. (d) Use Pythagoras theorem.
F sp3d hybridised.
25. (b, d) Both have planar geometry so possess
POS and both are geometrical isomers
18. (0) CO$ has maximum bond order which is
(different configuration).
3.5.
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Gaseous State
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24 CHEMISTRY
7. A 2 metre long tube closed at one end is lowered vertically into water until the closed end is flushed
w ith the water surface (see figure). Calculate the water level height (i.e. h). If vapour pressure of water
is negligible and 1 atm = 10 m of hydrostatic water head.
:::::::::::1...:.:.:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
::::::::::: h ::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
...............................................................................................
........... . .................................................................................
::j:::::: !1!!111!!1 :::::::::j::::::::::::::::::::::::j:::::j::::::::::::::::j:::::j::
....................................................................................................
....................................................................................................
....................................................................................................
(a) 1.01 m (b) 0.29 m (c) 1.71 m (d) 0.92 m
8. n moles of He gas is placed in a vessel of volume V litre at T K. If V1 is free volume of He, then the
diameter of He atom is
I I I I
(a) ( 3Vj
2rcNA n
)3 (b) [3(V - Vj)]3
2rcNA n
(c) [6(V - Vj)]3
rcNAn
(d) ( re: ny
9. Which sequence(s) of ease of liquifaction of gases is/are correct?
(b) CH4 > CO2 > H 2 0
(a) (::t-(:;L-(:;t =0
(ill
11.
Numeric Value Answer
The value of b for NH 3 and CS2 are given as 0.03713 and 0.07262 respectively (L/mol). Calculate the
ratio of molecular radii of the gases (Give answer till two decimal place).
•
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Gaseous State 25
12. In the following arrangment, find the pressure of the confined gas (in cm of Hg).
p = 13.6 gm/cc
(..__~
~ i_r_ _.___H_
g ____.__~O
I
1 atm
~ 40cm ➔
If the tube is held vertical keeping the open end up, length of air column shrink to 19 cm. Length in
cm by which the Hg column shift down is
14. A mole of CC14 vapours at 77 °C occupies a volume of 16 L. Tf vander-Waal 's constant are a = 20.19
L2 atrn mol-2 and b = 0.1383 L mo1- 1 . What will be compressibility factor at low pressure region?
15. The density of vapour of a substance (X) at 1 atm pressure and 500 K is 0.8 Kg/m 3 . The vapour effuses
through a small hole at a rate of 4/5 times slower than oxygen under the same condition. What is the
compressibility factor (z) of the vapour?
( I ) Integer Answer
16. What would be the value ofvan-der-waal constant 'a' w hen b = 0? Here Pis in atm and Vis in
litre/mol.
•
30
i~~···-········~·
~ 15 11
2 3 4 5 6
l/V ~
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26 ===================== CHEMISTRY
17. Which of the following velocity distributions belongs to the gas with highest molecular m ass if all the
m easurements were done at same temperature.
i 0.8
.c
:; 0.6
.g
.£J 0.4
2
0....
0.2
Velocity ~
18. In the following figure, when the two stopcorks are opened, the total pressure inside the flask will be
. be the value of x.
-10 what will
X
Stopcork- 1 Stopcork-2
20 . .
The equation o f state fior a certam
. gas 1s
. p =---
RT -a , w h ere ' a ' an d ' b' are constants
V,llb vm
distinct from zero. As certain w hether the gas has a critical point or not. A nswer as
(1) if the gas has critical point and as (2), ifno critical point.
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Gaseous State 27
Column-I Column-II
•
Match the parameters in left column with the parameters in the right column on which they depend :
23. The ratio of coefficient of thermal expansion a =( dV) IV and the isothermal compressibility
K = -(dV) IV for an ideal gas is dT P
dP T
p p T T
(a) (b) (c) (d)
T T p p
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28 CHEMISTRY
Passage-II
Gases show ideal gas behaviour in Boy le temperature range. Assume for the air this temperature range
between 300 K to 900 K.
An op en vessel at 27 °C is heated untill 315 th of the air in it has b een expelled. Assuming that volume
of vessel remains constant.
25. The temperature a t which vessel was h eated
(a) 750 K (b) 400 K (c) 350 K (d) 620 K
26. The escap e out if vessel is heated at 900 K
(b) !!__
2n (d) n
(a) n (c)
3 3 2
RESPONSE SHEET
1. (i)@(s)@ 2. (i)@(s)@ 3. (i)@(s)@
4. (i)@(s)@ 5. (i)@(s)@ 6. (i)@(s)@
7. (i)@(s)@ 8. (i)@(s)@ 9. (i)@(s)@
10. (i)@(s)@ 11. 12.
19. 20.
ANSWER KEYS
1. d 2. C 3. a 4. a 5. d 6. a 7. C
. . ~-
_. \
' I I ' I I
·------
1. (d) Suppose vessel (X) contains 0.5 mol each of Mol fraction ofC12 0 7 = 0.285
----- ·
CO and CO 2 and vessel Y is evacuated
Y c,
2 01 = 1- a {71 = 0.285; a= 0 _2
0.5molCO~ Yc1
2
a ~183 0.115
0.5 mol CO2 ~
dP dP
3. (a) -~oc(P- l)or -~=K(P - 1)
On opening the stop cock, the gaseous mixture dt dt
effuses into Y. 1
- _____!}!_ = Kdt · f P - dP = Kf dt
If x is the number of moles of CO effused in (P-1) ' Po P-l
0
time tout of a total of A moles effused, then M 2
the mean molar mass of the gaseous mixture log(Po - l) = Kt
P-l
remaining in vessel (X) is given by
M 1A + M 2 (1 - A) = 36 171.8 - 1
Now, l o g - - - = 7 x 10-7 x 10 x 24 x 3600
P- 1
2. (c) Cl2 0 7 (g)~Cl2 (g)+ 3.502 (g)
After solving, P = 94.33 atm
1-a a 3.5a
Now, let x be the mol fraction of Cl2 in the 4. (a) Cl2 + 3F2 ~ 2ClF3
gaseous mixture being analysed
1-a 3-3a 2a
Total moles at equilibrium = 4 - 2a
Yo2 =3 .5
06
fn
= · ; x=0.115
Yc1
2
~32 x Molar mass of equilibrium mixture
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30 CHEMISTRY
1-a 4x-n -
3 2
4 (d) 3
V-Ji'i
xNA = - -
n
Xc 1 = - - =0.207
2 4-2a
= m (air) - m (gas) - m (balloon) present. Out of cis and trans isomers, cis is
more polar than trans.
= 40.20 - 1.36 - 10 = 28.84 g
10. (b, c, d) See passage - 1
6. (a) On evaporation few amount of liquid is
converted into vapour phase 4 3
h -nr1 x4NO 3 h
11. (0.80) '-'l
- = ---- ⇒ - = -
3 '1 '-'l
bz ~nr] r] bz
Vapour i :::-,liquid 3
x4NO
i ---·
I I
10 5 cm 0
_1_=(!!1_)3 =(0.03713)3 =-t'0.51 129
Volumeof vapour=rcr2h =3.14 x (0.56)2 x 5 r2 b2 0.07262
h = 1.71 meter
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Gaseous State 31
13. (10) Suppose initially length of air column So, from equation (1)
22. A➔ q, r; B ➔ s; C ➔p;D ➔ q
Whenb=0,
3
PV =-!!_+ RT
V
... (1)
Avg. translational K.E. per mo! =
2 RT
3RT
& for per gram = - - - - -
1 2 x molar mass
When - =3, PV=20,
V
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32 CHEMISTRY
RT n = 2 (2 mo! of BF3 )
23. (b)PV=RT ; V = p
nb = 0.1 ; b = 0.05
n x 300 = ( n - in ) x T ; T = 750K
(X p
=
K T 300 x n = 900 x n 2 ; n2 = -1 n
3
24. (a) From the equation, No. of moles escape out
nRT= 2RT 1 2
=n - -n = -n
3 3
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Chemical
Energetics
1
C(s) + - O2 (g) ➔ CO(g); ~H = - 28 KCal
2
(a) - 83.23 KCal (b) - 92.42 KCal (c) - 84.24 KCal (d) - 90 KCal
2. A Carnot engine works between 120 °C and 30 °C. If the power produced by the engine is 400 watt.
What is the amount of heat absorbed from the source?
(a) 1625 watt (b) 1840 watt (c) 17 11 watt (d) 1747 watt
3. If the pressure and density of CO 2 gas in adiab atic process changes from (P 1, d) to (P 1, d 1) where
P = 32P 1 then dld 1 is equal to
I I I
(a) 1 )1.3
( -32
3
(b) ( 312 y-~ii (c) (32)1.33 (d) (32)!.4
4. One mole of a gas at 100 K is compressed isothermally from 20 dm3 to 5 dm3 . What will be the work
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34 CHEMISTRY
Given, B.E. of N 2, N - N and N = N are 942 KJ/mol, 170 KJ/mol and 420 KJ/mol.
If resonance energy of the product molecule of the given reaction is - 140 KJ/mol. What would be
MI
1 of the reaction?
(a) 812 KJ/mol (b) 715 KJ/mol
(c) 614 KJ/mol (d) 916 KJ/mol
/p'. /p'. /p'.
6. P+P--+ - P
'. p / '.p/
?
p - ·-p
'.p/
P- I I 11H = - 104 KJ/mol of P4
Solid white phosphorous undergoes polymerisation to give red phosphorous. What would be the bond
enthalpy of P - P bond in red phosphorous joining the two units of white phosphorous? Given that
enthalpy of sublimation of white phosphorous is 59 KJ/mol and enthalpy of atomisation is 316.25 KJ/mol
of P(g)
(a) 41 6 KJ/mol (b) 298 KJ/mol
(c) 305 KJ/mol (d) 513 KJ/mol
7. Calculate the work done when a system raises a column of water of radius 5.0 mm through 10 cm
(a) - 5.37 X 10-3 ] (b) 2.87 X 10- 3 ]
!ill
10.
Numeric Value Answer
Assume that human body is a heat engine. For a food intake equivalent to 1.0 x 107 Joule per day, a
human can work for 6.2 hour per day at a rate equivalent to 0.0374 HP (1 HP= 746 W). W hat is the
•
efficiency (in percentage) of human body?
11. One mo! of an ideal gas CP = 4R at 300 K is expanded reversibly adiabatically to n times the original
volume. What is the value of n if temperature falls to 75 K?
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Chemical Energetics 35
12. One m ole of an ideal monoatomic gas is caused to go through the cycle shown in figure. Then, the
change in internal energy in expanding the gas from a to c along path abc is xRT0 . Calculate x?
C
2PO ----------------------------------
l~
:::l
"'
£ po --------~-j i, b
I
V0 4V0
Volume ~
and 11H = 1800 cal/mo! respectively. The heat of combustion of I-butene is - 650 Kcal/mo!. Determine
the heat of combustion of trans-2-butene. Data B.E . of C = 0 = 196, 0 - H = 110, 0 = 0 = 118, C - C
= 80 and C - H = 98 Kcal/mo!; Aflv (H2 O) = 11 Kcal/ mol.
( I ) Integer Answer
14. If a gas expands adiabatically at constant pressure such that T oc
a : 2. The value of a is
•
v- 112 . The value of Cp: Cvfor it is
15. The heat evolved on combustion of 1 gram of starch, (C6H 10O 5)x into CO 2 (g) and H 2O(l) is 4.6 KCal.
Heat of formation of CO2 (g) and H 2 O(l) are - 94 .2 and - 68 .4 KCal/mol respectively. The magnitude
of standard enthalpy of formation of 1 g of starch (in KCal) is
16. An isobaric process, the ratio of heat supplied to the system and work done by the system for a
diatomic gas is a : 2. What is the value of a?
17. A solution of 6.3 g of haemoglobin (Molar mass 64000 in 25 ml of solution shows a temperature rise
of 0.03°C for complete oxygenation. Each mol of haemoglobin binds four moles of oxygen. If the heat
capacity of the solution is 4.2 J/K. ml, then the amount of heat released per m ol of oxygen bound (in KJ) is
18. A solution of 500 ml of 2M KOH is added to 500 ml of 2M HCI and the mixture is well shaken. The
rise in temperature T 1 is noted. The experiment is again performed for 250 ml KOH and 500 ml HCI
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36 CHEMISTRY
21. Which of the following is incorrect for the charge shown below ?
aA+bB
c,.,s; cC+dD
(298K) (298K)
~rs; j, i ~rs;
aA+bB
c,.,s; cC+dD
(OK) (OK)
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Chemical Energetics 37
(at 25°C)
Passage-II
RESPONSE SHEET
1. ~®@@ 2. ~®@@ 3. ~®@@
4. ~®@@ 5. ~®@@ 6. ~®@@
7. ~®@@ 8. ~®@@ 9. ~@Cs)@
10. 11. 12.
19. IAI 1
8 1 lcl lnl 20. IAI 1
8 1 lcl lnl
21. ~®@@ 22. ~®@@ 23. ~@Cs)@
24. ~®@@
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38 CHEMISTRY
ANSWER KEYS
1. b 2. d 3. C 4. a 5. d 6. C 7. d
8. a, b, c 9. a, b 10. 6.23 11. 64 12. 10.5 13. 603.25 14. 3
15. 1 16. 7 17. 8 18. 3 19. A - p , q; B - q, s; C - q, r; D - q, s
x+½(¾-x) = 1.06
W = 2.303 x 8.314 x l00log10 (
2
5
°)
X = 0.87 - 0.384( 1 3 1 3)
5x l0- 2o x 10-
Heat liberated by 1st reaction
= 0.87 (- 94) W = 1094.96 J
= - 81.78 KCal 5. (d) ~H 0 reaction = 3 x 942 - 3 (170 + 420)
= 1056 kJ/mol
Heat liberated by 2nd reaction Theoritical ~ HJ of product= 1056 kJ/mol
=( ¾- 0.87 )c- 28) = - 10.64 KCal (~H f )Exp· - (~H f hheoritical = - 140KJ
W WW.JEEBOOKS.I NI
Chemical Energetics 39
7. (d) The centre of mass of column lies half way 12. (1 0.5) PV = nRT at point c
along its length. Therefore, the centre of mass
2P0 x 4V0 = 1 x RTc
is raised to a height ( 1) . ⇒ T = 8PoVo
C R
Work = - m x g x height At point a,
= - volume x density x g x height PoVo
22 10 ⇒ T0 = -- ⇒ Tc = 8T0
Work = - (0.5)2 x l0 x l x 980 x R
7 2 Change in internal energy = nCr,4T
volume
For path a to b
= - 38.5 x 10 3 erg = - 3.85 x 10-3 J . 3 9
= 1x R x[3T0 ] = RT0
8. (a, b, c) For cyclic process, initial and final 2 2
temperature is same, hence, l'!.T i.e. T2 - T1 = 0 For path b to c
In Adiabatic free expansion, 3
q = 0, w = 0 ( ·: P ext = 0) = Ix - R x4T0 = 6T0 R
2
So, from 1st law,
Total change
!'!.U = q + w ; !'!.U = 0
·: !'!.U = 0 hence !'!.T = 0
9 2IRT0
= - RT0 + 6RT0 = - - = I0.5RT0
9. (a, b) For adiabatic process, qsys = 0 2 2
Hence, q smT = - q sys = 0 13. (603.25)
So, !'!.Ssmr = 0 ~ ~ F\ ~H = +0.95 Kcal
q sys ( . )
= -
!'!.S
sys T- + x Entropy- generat10n ~ H = + 1.8 Kcal
·: qsys = 0 so !'!.Ssys = x
·: Entropy generation is always +ve, hence,
!'!.Ssys= +ve ~ + 602 ~ 4C02 + 4H20 ~ H = --647.2 Kcal
10. (6.23) Intake = 1.0 x 107 J per day ~ + 602 ~ 4C0 2 + 4Hp (l)
0.0374 HP= 0.0374 x 746 = 0.0374 x 746 J/s
Output (work)= 0.0374 x 746 x 3600 Jh- 1 4Hp (l) ~ 4H20 (g) ~H~ = + 11x 4 = +44Kcal
= 0.0374 X 746 X 3600 X 6.2
~ + 60 2 (g) ~ 4C02 (g) + 4H20 (g)
= 6.23 x 105 J per day
~H = --603.25 Kcal
Efficiency
5 !'!.He = - 603 .25 Kcal
= Output x l00 = 6.23xl0 x l00 = 6 _23 1 1
intake 1.0 x l0 7 14. (3) T oc V 2 or T.V 2 = constant
11. (64) ·: Cp = 4R, hence from Cp -Cv = R ·.- for adiabatic process Tvr - I constant.
Cp 4R 1 3
Cv =3R and y= - = - =1.33 So, y - 1 = - ; y =
Cv 3R 2 2
Cp
3 a
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40 CHEMISTRY
Molar m ass of starch = (72 + IO + 80).x = 162.x 19. A - p , q; B- q,s; C - q, r; D- q, s
So, !1H = - 162.x/162~ = - I Kcal/gram _ n1 ( Cp ) 1 + n2 ( Cp h
1
16. (7) Work done by the system = - ve (Cp)mixing
We have to calculate,
q (heat absorbed) _ ( 1x ¾R)+(2 x iR)
- W (w.d. by the system) 1+2
q q nCpl:!..T Cp 23
= -~- = -----=--- = - R for 0 2 & 0 3 mixture.
- W q - 1:!..U nCpl:!..T - nCvl:!..T Cp - Cv 6
20. A- p , r; B - q, s; C - q, r; D - q, s
7 In (B) , No. of particles are decreasing due to
- R 7
2 complex formation of K 2[HgI4]
= =
7 5 2
- R- - R 2KI + HgI 2 ~ K2 [Hgl4 ]
2 2
4- ions '3-ions
v-' ' - -3
-y ---J
ions
Hence, a = 7
= 9.84 X 10-5
64000
= cs; + ds; -0 - 0 cs; + ds;
=
Heat released by this haemoglobin 22. (d) I2 is solid at room temperature and Br2 is
= 25 X 4 .2 X 0.03 = 3. 15 J liquid. Hence, F 2 and Cl2 will have m ore !1S
Heat released per mol of haem oglobin than Br2 and I 2 as these are gases at room
= 3.15 X 9.84 X 10-5 = 32000 J temperature.
Heat released per mol Similarly, C 6H 6 is liquid at room temperature
32000 while He, SO 2 and SO 3 are gases, so these
02 = - - = 80001 = 8 KJ
4 gases will have more entropy than benzene.
18. (3) Equivalents of KOH in 1st experiment In (a) part pentane will have more !1S than
= equivalents ofHCl cyclopentane as cyclopentane can not acquire
= 2 X 500 X 10-3 = 1000 X 10-3 various conformations because of angular strain.
Heat released in 1st experiment is In (d), butane can have various conformations
= 13.6 x 1000 x 10-3 Kcal. but in butane rotation about double bond is
q = m S 11T restricted so it will have lesser number of
13.6 x 1000 x 10-3 = 1000 x S x T, ... (1) conformations and hence it will have lesser
(assuming d = l g/c.c.) value of !1S than butane. Hence (d) is correct.
In 2nd experiment KOH is limiting reagent. 483.636
23 . (c) 11H 1 = = - 241.818 KJ/mol ofH2
Equivalent of KOH 2
= 2 X 250 X 1o-3 = 500 X 10-3 - 868.2
!1H2 = - - = - 289.4 KJ/mol ofH 2
Heat released in 2nd experiment 3
= 500 X 10-3 X 13.6 !1H 3 = - 347.33 KJ/mol ofH 2
q = m Sl:!..T - 483 .636
500 x 10- 3 x l3 .6 = 750 x S x T2 .. . (2) 24. (b) !1H 1 = =-15.llKJ/g ofO 2
32
Equation (1) divide by equation (2), - 868.2
!1H2 = - - - = - 18.09 KJ/g ofO3
7i 3 48
T2
=2
-347.33
11H3 =- - - = -10.22 KJ/g ofH2 0 2
Hence, x = 3 34
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Equilibrium
Step-I:
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42 ===================== CHEMISTRY
10. Which of the following relation(s) is/are true for alkaline solution?
Kw
(a) (b) pH > pOH (c) pOH < E__ (<l) pH < pOH
2
( I ) Integer Answer
16. A volume of30 mL of0.06 M solution of the protonated form ofan amino acid, methionine (H 2A+)
in titrated against 20 mL of 0.09 M NaOH . pH of resulting solution if pK01 = 2.28 pK02 = 9.72
•
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Equilibrium 43
17. Total number of aqueous salt solutions whose pH are independent of their concentrations are :
CH 3 COONa, KCl, CuCN , CH 3 COONH 4 , NH4 Cl, Sodium lactate, FeC13 , Cu SO4
18. An acid base indicator has K Hin value of 1.2 x 1o-3 . The acid form of this indicator is red and the basic
form is blue. The change in [H+] required to change the indicator from 60% red to 60% blue is 1o-x
mol/litre. What is the value of x?
19. 0.1 mol of H 2 and 0.2 m ol of CO2 are introduced in a closed vessel at 723 K and 50.67 KPa
H 2 (g) + CO 2 (g) ~ H 2 O(g) + CO(g) ... (1)
Analysis of the mixture shows that it contains 10 mol % ofH 2O(g). A mixture of CoO(s) and Co(s) is
then introduced such that the additional equilibria are established
CoO(s)+ H 2 (g)~Co(s) + H 2 O(g) ... (2)
CoO(s) + CO(g) ~ Co(s) + CO2 (g) ... (3)
Analysis ofnew equilibrium mixture shows that 30% (mol) ofH 2O(g) are present. What would be the
Kc for equation (2)?
20. Total number of solutions which will have p H greater than that of 0.1 M CH 3 COOH (Ka = 10- 5)
(i) 0. 1 M HCl
(ii) 0.1 M CH 3 COOH + 0. 1 M CH 3 COONa
(iii) 0. 1 M NH 4 OH (Kb = 10-5)
(iv) 0. 1 M CH 3 COONa
(v) 10-8 MHCl
(vi) 0.1 M CH 3COONH 4 (Ka = 10-5 & Kb = 10-5)
(vii) 0.1 M NaHA (K1 = 10-5 K2 = 10-7)
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44 CHEMISTRY
Passage-II
A 10-2 M solution of P4 O2 (NO 3) 2 was found to have pH of 3.8. Answer the following questions if
Antilog (- 3.8) = 1.6 x 10-4
25. What is hydrolysis constant for P4 o z2+?
(a) 2.56 x 10-6 (b) 3.7 x 10-6 (c) 4.9 x 10-6 (d) 3.7 x 10-8
26. What is the value of Kb for P4 O 2 .0 H© ?
(a) 10-6 (b) 3.9 x 10-8 (c) 4 X 10-? (d) 3.9 x 10- 9
RESPONSE SHEET
1. (i)@(s)@ 2. (i)@(s)@ 3. (i)@(s)@
4. (i)@(s)@ 5. (i)@(s)@ 6. (i)@(s)@
7. (i)@(s)@ 8. (i)@(s)@ 9. (i)@(s)@
10. (i)@(s)@ 11. 12.
19. 20.
ANSWER KEYS
1. C 2. a 3. a, b , c, d 4. a 5. a 6. a,b, c, d 7. b
8. a 9. d 10. a, b,c 11. 2.82 12. 74 13. 10.2 14. 9.8
15. 10 16. 6 17. 2 18. 3 19. 9 20. 6
2
4.0 = pKa + log 0Cz = pKa + log __3Q_ ... (2)
C1Vi - 20Cz Vz - 20 1 k a -k b
2
After solving, x = --"---=--
k1 +k2
5.0= PKa +log 30Cz = PKa +log_'.3_()_ .. .(3)
CiVi -30C2 v2 -30 5. (a) The step II is slow since K 1 and K 2 are very
high.
From equation (2) and (3) after solving
10
540 _[A]2 _ K _10 _
V2 = ~ =31.76ml K c - - - - -1- - - - 1 0
17 [Az ] Kz 109
From equation (2),
[A] = ✓[Az] xlO
20
4=-logKa +log - - - -
31.76-20 Rate = K[A][C] = K✓[A2 ] x 10 [C]
K a = 1 . 7 x 10---4 5 = K✓lOXlO X4;K = 0.125
2.
6. (a, b , c, d)
HCl + NaCN ~ NaCl + HCN
Yc12 = l37.5 = 0.53; x = 038 Initially l0 x0. l 0 x0.l 0 0
YPCl3 71 X = I milimoles = 2
Ateqm. 0
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46 CHEMISTRY
. 80 V= l.92mL
Given that y = 0.l x - = 0.08
100 10. (a, b, c) For basic medium,pH > 7 &pOH < 7
K = y . 09= 0.08 Since, pKw = 14 hence, for basic medium.
c (x- y)(0. l - y)' · (x-0.08)(0.1-0.08)
pH> pKw / 2 orpOH < pKw 12
4
0 9 = - - - · x=452M 11. (2.82)
· (x-0.08)' ·
[Al(HiO)d+ +H20 (l)~[Al(H20)sOH]2+ (aq)+H3 O+(aq)
Kz
CoO(s) +H2 (g) ~ Co(s) + H 2O(g)
-x +x
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48 CHEMISTRY
620
:. P = - x l 5 = 31 atm of 10 mole ofNH3 at 620 K
pOH = 3,pH = 11 300
Now, NH3 is dissociated to attain 50 atm at 620 K.
1 1
For (iv) pH= 7--logKa +-logC;pH = 9 Thus, P CY:.n orl0 CY:. 31
2 2
10 + 2x CY:. 50
For (v) [H+] = 10-8 [HCl] + 10-7 [water]
2x = 6. 13
= l.l x lo-7 2x 6.13X100
:. a= - Xl00 = - - - - = 61.3%
pH= 6.9586 10 10
1 1
For (vi) pH= 7- -logKa +-log Kb= 7 24. (d) K = nN2 x(nH2)3 x[_!__]2
2 2
P (nNH )2 Ln
Ka Ka 3
. ') p I +p 2 5+ 7
For (vu p H = - - - - - = - - = 6
2
Hence, except 0.1 M HCl, rest all solutions
2
T x [6.l~ x 3J [ 50 ]2
2 1. A- p, q, r ; B - r; C - p , q; D - s = l.528x103 atm2
22. A - s ; B - p ; C - q; D - r
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The Solid State
2. What fraction of the Ca atoms lies on the surface ofa cubic crystal that is 1.0 cm in length, if the radius
of Ca atoms is 96 pm and it crystallizes in bee arrangement
(a) 1.11 x 10-8 (b) 2.3 x 10-5 (c) 2.3 x 10-8 (d) 1.11 x 10-8
3. What will be the void space in closest packing of 'n ' spheres of radius 'l' unit, 'n' spheres of radius
0.414 units and 2n spheres of radius 0.225 units
(a) 15% (b) 18% (c) 19% (d) 32%
4. FeO is doped with 0.2 moles of Al2 0 3 number of cation vacancies will be :
(a) 0.1 NA (b) 0.2 NA (c) 0.3 NA (d) 0.4 NA
5. The sublimation temperature of a substance is - 83°C. It exists as cubic close packed structure with
unit cell edge length of 5.0 A and density 8/3 g/cm3 at - 100 °C. What would be the density of
substance at 0 °C and 1 atm assuming NA = 6 x 1023
(a) 50 g/cm3 (b) 2.23 g/cm3 (c) 2.23 g/litre (d) 1.86 g/litre
6. In a hypothetical solid, 'C' atoms from ccp lattice. 'A ' atoms occupy all tetrahedral voids and 'B'
atoms occupy all octahedral voids. The plane shown in the figure will looks like
7. There are three cubic unit cells A, B and C. Crystal A is fee and all of its tetrahedral voids are occupied.
'B' is also/cc and all of its octahedral voids are also occupied. 'C' is simple cubic and all of its cubic
voids are also occupied. If voids in all unit cells are occupied by the spheres exactly at their limiting
radius, then the order of packing efficiency would be
(a) A < B < C (b) C < A < B (c) C < B < A (d) A < C < B
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50 ===================== CHEMISTRY
8. In anfcc unit cell, atoms are numbered as shown below. The atoms touching each other are :
4
1 3 •
.··•·························
....····
...
2
(Atom numbered 3 is face centre of front face)
(a) 3 and 4 (b) 1 and 2 (c) 1 and 3 (d) 2 and 4
9. Following three planes (P1, P 2 , P 3) in anfcc unit cell are shown. Consider the following statements
and choose the correct statement.
........................
//
~
11.
12.
Numeric Value Answer
The number of square faces in a truncated octahedron is
cell in diamond is 'y', then value of (x + y) = ?
.
KF has NaCl type structure. If radius of K+ and F- are
186
r;:; and
214
•
'x' and the number of carbon atoms per unit
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The Solid State 51
( I ) Integer Answer
16.
17.
and NaCl are
Consider the following cases
(a) Ge is doped with As (b) As is doped with Ge
•
Total number of antiferromagnetic substances am ong MnO, CrO 2 , Fe, NiC12 , MgFe2 O 4 , Fe 3 O 4 , C 6H 6
20. The total number of ions per unit cell in sphalerite (zinc blend) structure if there is a schottky defect
of one anion per unit cell, are?
g-..:
2 1.
Match the Following
Match the column-I with column-II :
RESPONSE SHEET
1. (i)@(s)@ 2. (i)@(s)@ 3. (i)@(s)@
4. (i)@(s)@ 5. (i)@(s)@ 6. (i)@(s)@
7. (i)@(s)@ 8. (i)@(s)@ 9. (i)@(s)@
10. (i)@(s)@ 11. 12.
19. 20.
ANSWER KEYS
1. b 2. a 3. C 4. b 5. C 6. C 7. b
8. a,c,d 9. a, b , c, d 10. c,d 11. 14 12. 400 13. 21 14. 24
15. 12 16. 1 17. 3 18. 4 19. 4 20. 4
21. A - p; B - q, r; C - q, s, t; D - q, r 22. A - p, q, r, s; B - q, s; C - p , r, t; D - t
23. a 24. d 25. b, d 26. a, b
:.,.,
l ':
1. (b) In NaCl stoichiometry 4 : 4 No. of square faces visible at one face of crystal
i.e. 1 : 1 (x: y) 10
-4
= = 2.03xl015
Ratio of coordination number 6 : 6 (221.7xl0- 12 ) 2
i.e. 1 : 1 (x: y)
In CaF2 stoichiometry 4 : 8
In NaCl, x : y and y : x are same hence, if ratio of No. of atoms on one face of the crystal having
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54 CHEMISTRY
3 3 4 3 4 3
4 X~7t(l) +4X~7t(0.414) ] 4x-nr +4x-n(0.414r)
n 3 3 B = 3 3 = 0.79
4[ 4
+ 4X2X-7t(0.225)
3
3
(;J
= 4 .58n
. 4.58n
% space occupied = ~ x 100 = 81 %
4v2n
= 0.4 moles
1 and 2 are not touching each other.
+2 +2 +2 1 and 3 are touching where centre to centre
Fe Fe Fe
distance is _!!___ .
✓2
Two mo!AJ+3 creates= 1 mo! of cation vacancy 2 and 4 touching each other where centre to
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The Solid State 55
Similarly, 17. (3)(b), (c) and (e) are the example of p -type
8 x l4 semiconductors.
2.23 = ; a = 4.36A
3 23
a x 6.022 x l0 18. (4) The definition of truncated is cut short.
Bond length of Si - Si bond = ✓3a = 1.88A After cutting the dotted region in the picture
4 will look like t,.. i.e. trigonal face.
Because bond length of C - C is less than
Si - Si, thus, C - C bond will be stronger than
Si- Si bond.
11. (14) In truncated octahedron, all the com er of
octahedron become square face and hence its
number = 6 and number of C-atoms per unit (Tetrahedron)
13.
(400) -vu = v2 ✓
c21) 0 2
-
2 + ✓2 = 400 pm
=~+i = 4
⇒ 0 _92 =
6 x 10
23
( 2x
Z X18
r
_ [ 4 X¾1t(l.3)3 ]+[8 X11t(0.39)3]
14. (24)
- [ 4(1.3;t-39)
_ [ 4 X¾1t(l.3)3 +2(0.39)3 ]
- ( 4)3 (1 .69)3
8 X 3 X 1 = 24. 3✓3
15. (12) Tetrahedral voids = 2 (z) = 8
Octahedral voids = z = 4
= ✓31t(2.315) = 0.65.
4(4.826)
16. (1) Only MnO is antiferromagnetic.
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56 CHEMISTRY
24. (d) Minimum distance between two Cu atoms Since, observed density is lesser than that of
Minimum distance between a Cu atoms remains same. This crystal can 't have defect
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Compression
80°C 80°C
Volume of equilibrium mixture was reduced to 50 ml. Assuming that no condensation occurs and
temperature remains same, what will be the final partial pressure of 0 2 gas
(a) 810 torr (b) 360 torr (c) 760 torr (d) 715 torr
7. 1
Resistance of MgCl2 at 27 °C is 100 0. Cell constant is 0.01 cm- . If molar conductance of this
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58 CHEMISTRY
solution is 10 n- 1 cm2 mo1-1 then osmotic pressure of this solution after the addition of 0.6 gram of
urea in 1 litre ofMgC12 solution will be
(a) 1.24 atm (b) 0.4926 atm (c) 0.3624 atm (d) 0.9852 atm
8. Which among the following solution will have more boiling point than 0.1 M CH3COOH
(a) 0.1 M CF3 COOH (b) 0.1 M CC13COOH
OH
0 2N ~ N 02
(d) 0.1 Mof ~
9. Consider the following two diagrams : N02
Solvent o
Solvent •
(I)
Suppose that the solute molecules on the surface of solution occupy 10% of the surface area. The
correct statement is (are)
(a) If the water in the left vessel (I) was transferred to a container with 10% less surface area, the
vapour pressure would be lowered to same value as the vapour pressure in vessel (II).
(b) Mol fraction of solute in (II) is 0.33
( c) Boiling point of solution (II) is 114.44°C
( d) If the cross-sectional area of surface of solution in container (II) is increased by 10%, the number
of molecules in the vapour phase will increase by 10%
10. Consider 0.1 m aqueous solution of two solutes X and Y. The solute X behaves as a univalent
electrolyte, while Y dimerises in solution. Which of the following statement(s) is/are correct regarding
these solutions?
(a) The boiling point of the solution of X will be higher than that of Y
(b) The osmotic pressure of the solution of X will be higher than that of Y
( c) The freezing point of the solution of X will be higher than that of Y
(d) The relative lowering of vapour pressure of both the solution will be the same
~
11.
12.
Numeric Value Answer
•
0.02 M KI and 0.01 M AgNO 3 aqueous solutions are mixed in 2 : 3 volume ratio. What will be the value
of depression in freezing point. (dsolution = 1 g/ml)
1 mol. of A and 1 mol of B are mixed to form ideal solution. (VP. of pure A = 20 torr, VP. of pure
B = 80 torr)
Calculate the total pressure when last drop of liquid is remaining?
13. Calculate molal depression constant K for water? Latent heat of fusion= 80 cal/gm, F.P. of water= 0°C.
1
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Liquid Solution 59
14. Air is saturated with water vapour having 1230 torr pressure if volume is doubled. Calculate new
pressure in container at equilibrium. (VP. H 2O = 30 torr)
15. A solute 'S ' undergoes a reversible trimerization when dissolved in a certain solvent. The boiling point
elevation of its 0 .1 molal solution was found to be identical to the boiling point elevation in case of a
0.08 molal solution of a solute which neither undergoes association nor dissociation . To what percent
had the solute 'S' undergone trimerization?
( I ) Integer Answer
16. Safrole is contained in oil of sassafras and was once used to flavour root beer. A 2.4 mg sample of
safrole was dissolved in 100.0 mg of diphenyl ether. The solution had a freezing point of 25.64 °C.
The freezing point of pure diphenyl ether is 26.84 °C and the freezing point depression constant K ,
1
•
is 8.00 °C/m. The molar mass of safrole is
17. Total number of mixtures which are the examples of positive deviation
C 6 H 6 +C 6 H 5 CH 3 , CH3 Cl +H2 O, 0 +CH3 COCH3 , DMSO+C 6 H 6 , DMF+CH 3Br,
CH 3 Cl + CH3 Br, C 2 H 5 OH + H 2 O, CH 3 COCH3 + H 2 O.
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60 CHEMISTRY
Column-I Column-II
(A) S 1 : 0 .1 M glucose ; S2 : 0 .1 M urea (p) S 1 and S2 are isotonic
(B) S 1 : 0.1 MNaCl ; S2 : 0.1 MNa2 SO4 (q) S 1 hypertonic to S2
(C) S 1 : 0.1 MNaCl ; S2 : 0.1 M KCl (r) S 1 is hypotonic to S 2
(D) S 1 : 0.1 M CuSO4 ; S 2 : 0.1 M Sucrose
RESPONSE SHEET
1. (i)@(s)@ 2. (i)@(s)@ 3. (i)@(s)@
4. (i)@(s)@ 5. (i)@(s)@ 6. (i)@(s)@
7. (i)@(s)@ 8. (i)@(s)@ 9. (i)@(s)@
10. (i)@(s)@ 11. 12.
19. 20.
ANSWER KEYS
1. b 2. a 3. C 4. a 5. d 6. a 7. d
8. a, b, d 9. b,c, d 10. a, b 11. 0.03 12. 32 13. 1.86 14. 630 torr
15. 30% 16. 160 17. 5 18. 4 19. 8 20. 2
.. . ..
\ I I \ I I
_ \ _
Hints & Solutions :
..
I :
•,g.,._ _ __
----- ·
1. (b) Total pressure = 737 torr & 3. (c) 1tv= n1RT + n2 (l+a)RT
(non-electrolyte) (Electrolyte)
P~20 = 707 torr
a is ' l ' for NaCl.
0
Punk:nown = 737-707 = 30 torr
4.92xl = [ ~ x0.082lx300] + 0.05 x 2 x 0.0821 x300
For immiscible liquids 200
nA PJ
- = - ⇒ --"--=- = --
~20 707 75 / 18 x = 20 g
n
B
n0
rB
Ro
Unknown
30 25 / M 4. (a) 7t = icRT ic = osmolarity
After solving M = 141.4 gram. That solution will have highest ' n' which will
have highest value of osmolarity.
0. 1 M Glucose 0.01 M NaCl 10-3 m MgC12
1
For benzene as solvent i = -
2 ic = 0. 1 ic = 0.01 x 2 ic = 10-3 x 3
3
Molality of aqueous solution xN
2
x76.48xl0 = 0.987
lOxlO00 ⇒ XN = 1.28 X10-S
= - - - - =0.84 2
118.5xl00
If n represents number of moles ofN2 in 1 litre
f:i.Tf =i Kf x m of H 2 0 i.e. in 1000/18 or 55.6 moles ofH2 0
⇒ 1.75 = iXl.86X0.84 ⇒ i = 1.12 n -5 n
XN = --- ⇒ l.28Xl0 = --
l+a=l.12 ⇒ a=0.12
2 n+55.6 55.6
[H+ ] =Ca= 0.84 x 0.12 = 0.1008 Moll lit :.n=7. 18Xl0-4 mol=0.718 x 10-3 millimol
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62 CH EMISTRY
l I
0.08
- .- x lO0 f.i.Tf = K f Xm = l.86x- - = 0.03.
5
7. (d) M = -R_A__
Am
12. (32)
= _l_ x 0.0l x lO00 = 10 _2
100 10
0.6
Moles of urea = - = 10
-2 A"' 1 mol {{{{{{{~ Vapour
60 B"' l mol
nV = n1RT + in2 RT, i = 3 for MgC12 } L iquid
10. (a, b) Vant Hoff's factor ' i ' for Xwill be more 160 ~ - - -~
⇒ PT = s ⇒ IPr = 32 torr l
than one while it will be less than one for Y.
Hence B.P., n: and lowering in V P. will be
more in X in comparison to Y.
⇒ 1200 x V = P2 x 2V
11. (0.03)d = 1 g /cc, m =M
: . P2 = 600 torr
Kl + AgN03 ~ KN0 3 + Agl ..!,
0.02x2 0.0l x 3 0 0 :. Total pressure = Gas+ Water vapour
0.04 - 0.03 0.03-0.03 0.03 0.03
= 600 + 30 = 630 torr.
i=2
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Liquid Solution 63
:. K J = 186 KKgmol- 1 Cl
14.
CO 2 + CC14 , ~ + CC14 , are the pairs
( 63 0 torr) 123 0 = p gas+ p water vapour Cl Cl
Pgas = 1200 torr.
As volume of container is doubled: where landon forces of attraction are present.
(i) VP remain same 21. A- p; B - q, r; C - r, s ; D - r , s;
(ii) gas pressure changes. 22. A - p; B - r; C - p; D - q;
15. (3 0%) 3S ~ S3 (A) Same concentrations
I 0
1-30. 0.
(B) Osmolarity :
m = O.l , !l.Tb = Kb X (0.08)
NaCl= 0.2 M , Na2 SO4 = 0.3 M
l-2a
i=-- (C) Osmolarity :
l
N aCl= KCl = 0.2 M
!l.Tb = (1- 2a.)Kb (0.1) = Kb (0.08)
(D) Osmolarity :
=> 1- 2a = 0.8 => 2a = 0.2 =>a= 0.1
8X2.4Xl0-3 / M
=> (26.84- 25.64) =
10o x 10-3 11000 Number of moles of particles fom1ed per mole
=>M = 160
of solute (ROH) is 3 soi = 3.
⇒ 48=60(-4
4+x
)+42(-x)
4+x
⇒ x = 8 moles of'B'
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64 CHEMISTRY
Number of moles of particles formed per mole 26. (c) N ow,
of solute (ROH) are four; i = 4 . PM= P2-XB +Pf ·Xy
l1T1 = iK1 xm = 4xx0.2 = 0.8x
12 8
=271X- - +92X- -
25. (a)Given, P=l79XB+92 12+8 12 +8
:. Py= 179x0+92 = 92 mm
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Electrochemistry
& Redox Titration
~ MCQs with One or More than One Option Correct
1. In 100 ml M CH 3COOH, 50ml M NaOH is added and after this a platinometer is dipped in this
10 10
•
resulting solution and H 2 gas at ' l ' atm pressure is passed by the help of glass jacket. What will be the
electrode potential of the resulting solution at 25 °C assuming that Ka for CH3 COOH is 10-5 7
(a) + 0.2955 volt (b) - 0.2955 volt (c) - 0.3456 volt (d) + 0.3456 volt
2. Calculate the value of solubility product for solid Agl by using following data :
Ag+(aq) + e- ~ Ag(s) E 0 = 0. 800 volt
Agl(s) + e- ~ Ag(s) + 1-(aq) E 0 = - 0 164 volt
(a) 5 x 10-17 (b) 6 x 10-15 (c) 2 x 10-14 (d) 4 x 10- 12
3. A half cell reaction: Ag 2 S+ 2e- ~ 2Ag + s2 - is carried out in a half cell PtAg S I Ag,H 2 S(0.1M), at
2
(solid) (solid)
pH= 3. What will be the electrode potential of this electrode ifE0 Ag+/Ag = 0.8 volt, Ka for H 2S is
10-21 and Ksp of Ag2 S = 10-49
(a) -0.1735V (b) -0.19V (c) +0. 1735V (d) +0.19V
4. Reduction of NOf ions occur as
e (±)
NO3 + 4H +3e- ~NO+2H 2 O ; E 0 = 0.96 volt.
The electrons are provided by cathode till that the solution originally having 0.1 M NOf and 0.4
M H® shows that 80% of NOf ions are converted to NO showing l bar pressure. The reduction
potential of remaining solution
(a) 0.84 volt (b) 1.36 volt (c) 1.08 volt (d) 1.56 volt
5. For the cell: Ag(s) I AgBr(s) I KBr(aq) II Hg2Bris) I Hg
the variation of emf with temperature is shown by the graph given below:
0.071
i
E
0.069
0.067
0.065 ,....____,•_ _ _ _ _ __
293 K 303 K
T ~
What will be LiH of the reaction ?
(a) 9.882 kJ (b) 12.762 kJ (c) 6.782 kJ (d) 13 .884 kJ
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66 ===================== CHEMISTRY
6. What will be hydrolysis constant of anilinium hydrochloride Pt 1H2 (1 atm) I HEB (1 M) II PhNH3 Cl
(M/32) I H 2 (1 atm), Pt if cell potential of the cell is - 0.188 volt at 298 K
(a) 1.352 x 10-5 (b) 4.32 x 10-6 (c) 8.72 x 10-5 (d) 7.98 x 10-4
7. Impure Cu contains only Fe, Au and Ag as impurities . After passage of 140 ampere for 482.5 seconds
the mass of anode decreased by 22.260 gram and the cathode increased in mass by 22.011 gram.
Calculate the % of iron in impure copper.
(a) 2% (b) 0.85% (c) 5.5% (d) 98.88%
8. Consider the following reactions:
A+B ~ C+D Kc = K 1 and E 0 = a volt
2A + 2B ~ 2C + 2D 0
Kc = K 2 and E = b volt
then select correct option :
(a) a = b (c) a = 2b (d) b = a 2
9. The tarnishing of silver ornaments in atmosphere is due to
10. A lead storage battery is discharged which causes the H 2 SO4 electrolyte to charge from a concentration
of 40% by weight (d = 1.260 g/ml) to 28% by weight. The original volume of solution was 1 litre.
Select correct statement(s)
(a) Overall reaction will be Pb(s) + PbO2 (s) + 2H 2 SO 4 (aq) ~ 2PbSO 4 (aq) + 2H 2 O(£)
(b) A total 2.0 moles ofH 2 SO4 is reacted.
(c) The total charge released from anode of the cell is 1.93 x 105 coulomb.
(d) The mass of electrolyte solution has decreased.
rfil
11.
12.
Numeric Value Answer
If an aqueous NaCl solution is electrolysed using a current of 5 A for 200 minutes, volume of Cl2 (g)
in ml, produced under STP conditions is (F = 96500 C).
Gold is to be plated out on a square coaster of side-length of 5 cm by electrolysis of a solution
•
containing K[Au(CN)2 ]. If thickness of gold plating is x x 10-2 mm by passing 2 A for 1 hour. What
is the value of x?
13. How many Faradays of electricity is required for electrolysis of 144 gram of acidified water?
14. Ag I AgBr I Br- I II Cl- I AgCl I Ag ; K sp of AgBr = 10-13 ; K sp of AgCl = 10-IO
(s) (s) (0.1 M) 0.0IM (s) (s)
Calculate Ecell at 25°C?
15. A lead storage battery contains 2L H2 SO4 solution (1.2 g/ml density and 40% W/W). During
discharging, density of H 2 SO 4 reduces to 1.1 gm/ml and % W /W = 20%.
Calculate amount charge (in F) produced keeping volume constant.
( I ) Integer Answer
16.
17.
Equivalent conductance of 0.2 M aqueous solution of a weak monobasic acid (HA) is 10 S cm 2 eq- 1
and that at infinite dilution is 200 S cm 2 eq-1 . Hence, pH of this solution is :
A 500 ml of aqueous NaCl solution is electrolysed for 1 minute using a current of 8 mA at 25 °C. What
•
is the pH of the final solution?
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Electrochemistry & Redox Titration 67
18. The charge required for discharging 115 gram ofNa from molten NaCl is .. .. Faradays.
19. Emf of a cell corresponding to the reaction.
Zn(s) + 2HEB(aq) ➔ z n+2(aq) (0.1 M) + Hi(g) (1.0 atm) is 0.3 175 volt at 25°C.
A lso, at 25°C, E 0 Zn+2/Zn = - 0.76 volt. The pH of solution in cathode chamber is.
20. A current of 0.01 A is passed through a solution of iridium bromide. The only reaction of the cathode is
the deposition of iridium metal. A fter 3.0 hrs, 0.072 g oflr is deposited. The oxidation state of iridium
ion (atomic weight= 192) is
Column-I Column-II
(A) E 0 (Fe+3, Fe) (p) - 0.70 volt
(B) E 0 (4H2O ➔ 4HEB + 4OH-) (q) - 0.40 volt
(C) E 0 (Cu+2 + Cu ➔ 2Cu) (r) - 0.04 volt
(D) E (Cr+3, Cr+2)
0
(s) - 0.83 volt
Passage-I
A current of 15 ampere is used to plate N i from N iSO4 bath. Both H 2 and Ni are formed at cathode. The
current efficiency ofNi formation is 60% (at wt . of N i is 58.71).
•
23. The thickness of plating if the cathode consists of a sheet of 4 cm 2 which is coated on both sides,
density of N i is 8.9 g/ml
(a) 0.276 cm (b) 0.272 cm (c) 0.316 cm (d) 0. 138 cm
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68 CH EMISTRY
24. The volume ofO2 is formed per hour at S.T.P.
(a) 6.26 litre (b) 3.1 3 litre (c) 9.39 litre (d) 2.51 litre
Passage-II
Redox reactions play a pivotal role in chemistry and biology. The values of standard redox potential (E0 ) of
two half-cell reactions decide which way the reaction is exp ected to proceed. A simple example is a Daniel
cell in which zinc goes into solution and copper gets deposited. Given below are a set of half cell reactions
(acidic medium) along with their E 0 (V w ith respect to normal hydrogen electrode) values. Using this data
obtain the correct explanations to questions given.
12 + 2e- ➔ 21- E 0 = 0.54 volt
Cl2 + 2e- ➔ 2c1- E 0 = 1.36 volt
Mn+3 + e- ➔ Mn+2 E 0 = 1.50 volt
Fe+3 + e- ➔ Fe+2 E0 = 0.77 volt
Oz+ 4H© + 4e- ➔ 2H2 O E 0
= 1.23 volt
25. Select correct statement.
(a) Chloride ion is oxidised by 0 2 (b) Fe+2 is oxidised by iodine
( c) Iodide ion is oxidised by chlorine (d) Mn +2 is oxidised by chlorine
26. While Fe+3 is stable, Mn+3 is not stable in acidic medium because
(a) Oz oxidises Mn+2 to Mn+3 (b) 0 2 oxidises both Mn+2 and Fe+z
(c) Fe+3 oxidises H 2 O to 0 2 (d) Mn+3 oxidises H 2 O to 0 2
RESPONSE SHEET
1. (i)@(s)@ 2. (i)@(s)@ 3. (i)@(s)@
4. (i)@(s)@ 5. (i)@(s)@ 6. (i)@(s)@
7. (i)@(s)@ 8. (i)@(s)@ 9. (i)@(s)@
10. (i)@(s)@ 11. 12.
19. 20.
ANSWER KEYS
1. b 2. a 3. a 4. a 5. a 6. a 7. b
8. a, b 9. a, b 10. a, b, c, d 11. 6963 ml 12. 0.3 13. 16 14. 0.27V
15. 5.3 F 16. 2 17. 9 18. 5 19. 8 20. 3
\ I I
•' •
. . --
_... \
Hints & Solutions .I ..: :
• , g __ _ __
-----
1. [H+ ]2 [s2- 1 c10-3 )2 cs2- )
3. (a) K =- - - - - - - -
Moles = lOO x _!__ x l0- 3 1 -3 a [H2 S] 0.1
50x-xl0
10 10 ⇒ [S2- ] = 10- 16
= 10 X 10-3 = 5x 10-3
NaOH w ill be finished and resulting solution Because [Ag+] 2 [s2-] = Ksp
will fom1 buffer solution with 5 x 1o-3 moles of
[Ag+]2 10-16 = 10-49,
CH 3COOH and 5 x 10-3 moles ofCH 3COONa
(CH3COONa) [Ag+] = ✓10-33
pH=-l0gK + l o g - ----
a (CH3 COOH)
E = Eo + 0.0591 10 [A +]
-5 5 x l0-3 Ag+/Ag 1 g g
= - log 10 + log
5xlO-3 0.0591 -33
E = 0.8+--logl0
1
pH = 5, [H+] = 10-5
E = -0.1735 volt
By using Nerst equation
4. (a) NO3 + 4H$ +3e- ~NO+2H 2 O
0.05911 [ +] 0.05911 -5
E=E 0 + - - og H =0+ - - oglO
1 1 0.1 0.4 0 0
0.1 -x 0.4-0.4x X 2x
2. (a) Agl + e- ~Ag + 1-
t::..G0 = -nFE0 = +0.164F 80
x = - XO. I = 0.08
100
Ag~ Ag$ +e-; !1G0 = -nFE0 = +0.8F
After reduction,
By adding these two equations, we get
[N03] = 0.1-0.08 = 0.02
Agl ~Ag++ 1-; /1G 0 = 0.164F + 0.8F
[H+] = 0.4 - 0.32 = 0.08
= 0.964 F
0.059 NO-[H~
3
]4
-!::,.GO E=E +--log--0
--
logK = --- 3 (PNo)
sp 2.303RT'
4
lo K = - 0.964 x96500 = _ + 0.059 log(0.02)(0.08)
0 96
g sp 2.303x8.314 x 298 3 1
(araE)
[A][B] [A]2[B]2
0.07-0.066
- = - - - - =0.0004
P 10 K 2 = K 12 while a = b because E 0 is independent
of stoichiometry of cell reaction.
1
9. (a, b) 2Ag + -0 2 ➔ Ag2 0
2
=- 2 X 96500 (0.068 - 29 Q X 0.0004) 2Ag + H 2 S ➔ Ag2 S + H 2
= 9881.6 J = 9.882 kJ
10. (a, b , c, d) Net cell reaction of discharge is
6. (a) It is an example of electrolyte concentration
cell Pb+ PbOz + 2HzSO4 ➔ 2PbSO 4 + 2HzO
xmol xmol
0.0591 C (Cathode)
E = - - l o g2- Initial mass ofH2 SO4
n C1 (Anode)
40
0.0591 C2 -4 Wj_ = 1000 x 1.26 x - = 504 gram
-0. 188= - - l o g -, C2 =6.5 l x l0 M 100
1 1
Final mass of H2 SO4
i.e. [H+] due to salt hydrolysis of anilinium
hydrochloride is 6.51 x 10-4 28
W2 = (1260-98x+ 18x)x - = 352.8-22.4x
100
[H+] =Ch ; 6.51 x 10-4 = 1/32 h
From reaction,
h = 2.08 x 10-2 504 - 98x = 352.8 - 22.4x ⇒ x=2
2
Kh = Ch = __!__ (2.08x l0- 2 ) 2 11 . (6963 ml) Volume equivalent of Cl2 ( ~) = 11.2
32
Ve X it 11.2 X 5 X 200 X 60
= 1.352x l0- 5 V= - - ⇒ V=------lt
96500 96SOO
7. (b) It is the case of electro refining
:. V = 6.963 lt. = 6963 ml.
At cathode: Cu+2 + 2e- ➔ Cu
12. (0.3) Oxidation state of gold in the given
At anode: Cu ➔ cu+2 + 2e-
compound = + 1
Fe ➔ Fe+2 + 2e-
197
(Because both Cu & Fe are active metals) Equivalent mass of gold = - - = 197.
1
Equivalents at cathode
Wt. of gold deposited
. 140X482.5
= Equivalents at anode = - - - - = 0.7 E X it 197 X 2 X 60 X 60
96500 = 96500 = _ _9_6_5-00-- = 14·7 gram
Equivalents at anode= 0.7
Eq. of Cu+ Eq. of Fe= 0.7 14.7 3
Volume of gold plated = - - = 0. 76 cm
19.3
22.011 ~ = 0 7
63.5 + 56 .
-- - Surface area of coaster= 5 x 5 = 25 cm2
2 2
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Electrochemistry & Redox Titration 71
A B -l AB - E0
g+ r ~ g r+ e ; Ag lAgBr lBr- 1 [H+] = ca = 0.2 x 0.05 = 0.01
(s) 0.1 M (s)
Cathode: pH=2
E~ell = 0.059 X 3
One Na+ required one mol of e- i.e.
0.05911 -1
Ecell = 3 x 0.059 - - - og10 10 1 F of charge hence, 5 moles of Na will consume
1
5 F of electricity.
= 0.059x4 Volt= 0.236
19. (8) E:en =E=-E~ = 0 -(-0.76) =0.76volt
IEcell = 0.27 volt I
0 0.0591
Ecell = Ecell - --IogQ,
15. (5.3F)t=0, V=2L=2000mL n
2
d = 1.2 g/ml Q_[zn+ ]_ 0.1
- [H+)2 - [H+)2
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72 CHEMISTRY
E 0 (Cu +2 +Cu~2Cu+)
= 0.82 volt
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Chemical
Kinetics
~ MCQs with One or More than One Option Correct
1. A radioactive substance 'X' has half life of 2 hour. An injection contains 2 µg of 'X' is repeatedly
given to the patient for the treatment of cancer with the time interval of2 hour. How much amount of
•
'X' will be present in the body of patient just after 4th injection
(a) 8 µg (b) 3.125 µg (c) 3.75 µg (d) 6.5 µg
7
2. Cl2 0 7 (g)~Cl2 (g) +-02 (g) (first order)
2
When decomposition is carried out in a closed box, pressure measured after 15 minutes and after a
very long time were found to be 240 and 900 mm of Hg respectively. Calculate the pressure that would
be observed in the box after 140 min under identical codnitions of temperature
(a) 495.75 mm (b) 660 mm
(c) 450 mm (d) 461.5 mm
3. A reaction rate increases by a factor of 500 in the presence of catalyst at 37 °C. If the reaction is carried
out in presence of a catalyst at 127 °C by what factor, compared to original rate in absence of catalyst
at 27 °C, the rate will increase. In absence of catalyst activation energy is 106 kJ/mol.
(a) 8.33 x 105 (b) 2.04 x 105
(c) 5.05 X 106 (d) 3 x 106
4. Two radioactive nuclides A and B have halflives in the ratio 2 : 3 respectively. An experiment is made
with one mo! of each of them. Calculate the molar ratio of A and B after a time interval of three times
of half live of A
1 1
(a) (b)
2 4
1 2
(c) (d)
3 3
5. In order to determine the volume of blood in an animal, a 1.0 ml sample of solution of 103 dpm of
3
1H is injected into the animal blood stream. After sufficient time for circulatory equilibrium to be
established, 2 ml of blood is found to have activity to 10 dpm. The volume of blood in animal is :
(a) 20 ml (b) 150 ml
(c) 195 ml (d) 199 ml
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74 ===================== CHEMISTRY
6. Gaseous HI first adsorbed on the surface of gold and then undergoes decomposition into H 2 and 12 .
Which of the following graph correctly represents the reaction?
t----HI
p
t
p
t
p---HI
HI HI
Reaction coordinates ~
(a) 1 (b) 2
(c) 3 (d) 4
8. A reaction takes place in three steps; the rate constants are K 1, K 2 and K 3 . The overall rate constant
K = (Ki K 3 ) . If the energies of activation are 40, 30 and 20 kJ/mol, the overall E 0 will be if 'A' is
Kz
constant for all
23 K 23K
2 2 2 2
3[Ao]3(2 3 -l) 2[Ao]3(2 3 - l)
(c) 5
(d) 2
23 K 3x23 K
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Chemical Kinetics 75
(ill
11.
12.
Numeric Value Answer
•
A given sample of milk turn sour at room temperature (27 °C) in 16 hours. In a refrigerator at 7 °C, milk
can be stored three times as long before its sours. How long (in min.) it takes for milk to sour at 57 °C?
A wooden lamp excavated recently was found to emit 5~ particles per minute per gram of carbon. The
minute per gram of carbon. The freshly cut wood is found to emit 14~ particles per minute per gram of
carbon. Calculate the age of wooden lamp. Half life period of 14C 6 is 5760 years.
13. A substance (Bicyclohexene) undergoes !81 order decomposition. The decomposition follows two
parallel path as
~ Cyclohexene
Bicyclohexene
~ Methyl cyclopentene
k 1 = 1.26 x 10-4 s - I , k2 = 3.8 x 10- 5 s. What is the percentage distribution of cyclohexene and methyl
cyclopentene?
[A]4-_1_
1
- (t+ 1)
The rate of disappearance of 'A ' (in 10-6 M sec1) at the concentration [A]= 0.2 Mis?
( I ) Integer Answer
e K1
e e ow'
~
e e
OI + Cl is given below :
e
•
OCI + H 2O ~ HOCI + OH (fast)
K2
le+ HOCI~ HOI + Cle (slow)
K'
e __ ~ e
OH + HOI ~ H2O +OI (fast)
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76 ===================== CHEMISTRY
t t 1 - - - - - - [0 order]
I.
[O order]
II.
t
X
[O order]
III.
dx
dt
a~ a~ (a-x) ~
t (1.5 o rder)
t
..j(a-x) ~ Noc)
IV -
3 V
(a-x) 2
/ ~
i
C:
0
-~
~
u
C:
8
Time ~
th
Here, t corresponds to the time at which (¼) of reactant is decomposed. The value of ' n ' is
19. The half of a gaseous compound (A(g) ➔ B (g)) initially at 2 atm is 200 seconds. If the initial pressure
is taken as 1 atm, the half life reduces to 100 seconds. The order of reaction is
20. If for a reaction A ➔ products, the concentration of A are Co, aCo, a 2Co, a 3Co ..... after time interval
of 0, t, 2t, 3t .... where 'a ' is a constant and O< a < l. The order ofreaction is
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Chemical Kinetics 77
d[A] (a)
Column-III
!'!.H = + ve or - ve
•
---=---
~t dt
(B) Rate constant of reaction (2) Vt = Vt (b) !'!.H = - ve
(C) V .Vo.T
-- (3) Vt "'F Vo (c) t➔O
1
- 273
t
t 1/,
I
- Co ---+
(B) ~ (q)
t3 ! 4 = 2xt112
(C)
1112
I I/. - Co ---+
,
(r)
tI ~
'
i
-dc1
-
ct dt
I
I -
~ Time -+ ,
Time---+
(D) ' (s) t112 x c0 = constant
t
In c,
I -----
Time ---+
(t) Zero order
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78 CHEMISTRY
2-
Passage-I
e
S20 8 + 31 ~2S04 + 13
2- e
•
This reaction is of first order both with respect to persulphate and iodide ions. Taking the initial
concentrations as 'a' and 'b' respectively, and taking x as the concentration of triiodide ion at time 't',
a differential rate equation can be written.
Two suggested mechanisms for the reaction are :
I. (fast) ; (slow)
(fast)
3- k2 2- EB
II. (slow); S2 0 8I ~ 2S04 + I (fast)
k
(fast) ; 12 + l e ~ I3e (fast)
dx dx
(a) dt =k[a-x][b-3x] (k>O) (b) - =-k[a-x][b-3x] (k>O)
dt
dx dx
(c) - = k[a-x][b-x] (k > 0) (d) dt =-k[a-x][b-x] (k > O)
dt
(I)
dt 2 dt
Passage-II
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Chemical Kinetics 79
c.i
C
(a) (b) 8
t (sec) t (sec)
c.i c.i
C
0 C
(c) u (d) 8
[A ],
t (sec) t (sec)
26. If k 1 and k2 both are almost same then which graph in the above question is most suitable?
(a) Graph 1 (b) Graph 2 (c) Graph 3 (d) Graph 4
RESPONSE SHEET
1. Ci)@@@ 2. Ci)@@@ 3. Ci)@@@
4. Ci)@@@ 5. Ci)@@@ 6. Ci)@@@
7. Ci)@@@ 8. Ci)@@@ 9. Ci)@@@
10. Ci)@@@ 11. 12.
19. 20.
21. IAI 1
8 1 lcl lnl 22. IAI 1
8 1 lcl lnl
23. Ci)@@@ 24. Ci)@@@ 25. Ci)@@@
26. Ci)@@@
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80 CHEMISTRY
ANSWER KEYS
1. C 2. a 3. C 4. a 5. d 6. b 7. C
8. b 9. C 10. a,b,d 11. 240 12. 8441 13. 23.2 14. 16.48
15. 80 16. 2 17. 5 18. 5 19. 0 20. 1
: l:
·· ------ ------ ··
3
2.303log500 = (l0 6 - Ep) X l0
1. (c)N=No(½r
8.314X310
n = No.of half lives EP = 90 kJ/mol
n = Total time / 112
90xl03
pt 2nd 3rd 4th loge K p = loge A - - - - - ... at 400 K
No. of Dose 8.314X400
No. of halflife 3 2 1 0
106Xl03
loge K 0 = loge A - - - - - ... at 300 K
N = 2(½)3 + 2(½)2 + 2(½) 1 + 2(½)o 8.314X300
1 1
N = - + - +1+2 = 3.75 1O(Kp )400K _ 106 X 103 90 X 103
4 2
(K0 )300K 8.314X300 8.314X400
2. (a) Cl2 O 7 ~ Cl2 + 3.50 2
t=0 a 0 0
t = 15 min a- x X 3.5x ... 240mm
t = (X) 0 a 3.5a ... 900mm 4. (a) Let the half lives of A & B are 2a and 3a
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Chemical Kinetics 81
~ 0.693 0.693 -4 -1
/ \ , = - - = - - =l.22xl0 year
Reaction coordinates ~ t112 5760
11, 12 , 13 are intermediates formed during the :. t = 2.303 log N 0 = 2.303 log 14
reaction. "' Nt 1.22xl0-4 5
-Ea
= 8441 years
8. (b)K=AeRT
13. (23.2)
Cyclohexene 1.26 x 1o-4
-------= =3.32
Methyl cyclopentene 3 .8 x 10-5
-30
Percentage of cyclohexene
= Ae-(40-30+20)RT = AeRT
3.32
= --Xl00 = 76.8%
So, overall activation energy = 30 kJ/mol 4.32
1 Percentage of methyl cyclopentene
9. (c) + d[B] = - d[A] = k[A]3
dt dt = 100 - 76.8 = 23.2%.
14. (16.48) The time at whcih [B] is maximum,
[Ao]I Z d[A]
or
'
f -- = K Jof
I
t
112 dt
t=-l-lnk2 = 1 In~
IAol [A]3 k 2 -k1 k1 0.1-1/30 1/30
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82 CHEMISTRY
k = 3.( 1
t (a - x)
112
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3. In an adsorption experiment, a graph between " log (x/m) vs. log P " was found to be linear with slope
of 45°. The intercept on the y-axis was found to be 0.3010. What is the amount of the gas adsorbed per
gram of charcoal under a pressure of 0.5 atm.
(a) 1.0 (b) 2.0 (c) 3.0 (d) 4.0
4. One litre vessel having 20 gram charcoal (d = 2 g/c.c.) was filled with a gas at 300 K. The pressure of
the gas was 760 torr. Due to adsorption the pressure of gas falls to 608 torr. What is the number of gas
molecules adsorbed per gram of charcoal?
(a) 2.4 x 1021 (b) 2.4 x 1020 (c) 2_4 X 1022 (d) 2.4 x 1023
5. One gram of activates carbon has a surface area of 1000 m 2 . Considering complete coverage as well as
mono moleclular adsorption, how much NH 3 at S.T.P. would be adsorbed on the surface of 44/7 gram.
Carbon ifradius of a NH 3 molecules is 10-8 cm (NA= 6 x 1023 )
(a) 7.46litre (b) 0.25litre (c) 44.8litre (d) 25litre
6. A catalytic poison renders the catalyst ineffective beacause
(a) It is preferentially adsorbed on the catalyst.
(b) It adsorbs the molecules of the reactants.
(c) It always combines chemically with the catalyst.
( d) It combines with one of the reactant.
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84 ===================== CHEMISTRY
~
11.
Numeric Value Answer
•
The mass of gas absorbed x per unit mass of adsorbate m was measured at various pressure p. A graph
between log(:) and logp gives a straight line with slope equal to 2 and the intercept equal 0.4771.
15. For the coagulation of 200 mL ofAs2 O3 , 10 mL of 1 M NaCl is rquired. What is the coagulating value
of NaCl?
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Surface Chemistry 85
( I ) Integer Answer
16. Total number of statements which are correct regarding heterogeneous catalysis. •
(a) The surface of catalyst unlike the inner part of the bulk, has free valencies which provide the seat
for chemical forces of attractions.
(b) In last step of heterogeneous catalysis heating is must for desorption of product moelecules from
catalyst's surface.
(c) For hydrogenation reaction catalytic activity increases from group 5 to group 11 metal.
Catalyst
(d) In hydrogenation reaction maximum activity in shown by group 7-9 elements of periodic table.
(e) Porosity range of ZSM - 5 is 0.26 nn1 to 0.56 nm.
17. The gold number of gelatin is 0.01 . If the amount of gelatin to be added to 1000 ml of a colliodal
solution of gold to prevent its coagulation before adding 1 ml of 10% NaCl is 'x ' mg then 'x ' is
18. A ssuming haemoglobin as +ve sol, how many among the following can coagulate haemoglobin
Fe(OH)3 sol, Ca(OH) 2 , Al(OH)3 , Starch, Clay, As2 S3 sol, CdS sol, Basic dye.
19. 526.3 ml of 0 .5 m HCI is shaken with 0.5 g of activated charcoal and filtered. The concentration of
filterate is reduced to 0.4 m. Degree of adsorption (x/m) will be.
20. Among the following colloids the number of colloids having negatively charged colloidal particles is:
Soap solution of sodium stearate, solution ofAgCl obtained by mixing equimolar mixture of AgNO 3
and KCI, gold sol, Fe(OH)3 sol, Silicic acid sol, Basic dye, acidic dye, metal sulphide sol, PHBV in
acetone.
g-..:
2 1.
Match the Following
Match the columns :
Column I
(A) Placing silica gel in water vapour (p)
Column II
Enzymatic catalysis
•
(B) Placing anhydrous CaC12 in water vapours (q) Occlusion
(C) Placing finely divided nickel in closed vessel having H2 gas (r) Adsorption
(D) Conversion of proteins into amino acids (s) Absorption
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86 CHEMISTRY
RESPONSE SHEET
1. (i)@(s)@ 2. (i)@(s)@ 3. (i)@(s)@
4. (i)@(s)@ 5. (i)@(s)@ 6. (i)@(s)@
7. (i)@(s)@ 8. (i)@(s)@ 9. (i)@(s)@
10. (i)@(s)@ 11. 12.
19. 20.
ANSWER KEYS
1. a 2. a 3. a 4. b 5. a 6. a 7. a, b, c, d
8. b, c 9. a, c 10. b , c, d 11. 48 12. 900 13. 50 14. 0.03
15. 50 16. 4 17. 1 18. 4 19. 4 20. 5
'· ._
_...
\ I I
: l:
1
mass 6 - = tan 0 = tan 45° = 1 or n = l
--- = - =4 c.c. n
density 1.5
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88 CHEMISTRY
log k= 0.3010 so k= 2 Volume ofNH3 adsorbed at S.T.P.
2Xl023
Again from ~ = kp 11n; - - - x 22.4 = 7.46 litre
m 6xl023
X
- = 2 X (0.5) 1 = 1.0 6. (a) Informative
m
microscope.
Moles of gas adsorbed
9. (a, c) NaCl forms true solution while Tyndall
__(_7_60_-_60_8_)_X_9_90_ _ = 8 _04 X _3
10
760 xlO00x 0.0821 x 300 effect is the property of colliods.
4.8 X 10 21
- - - - = 2.4 X 10 20
20 --------------------
1og k = 0.477
44 7 2
5. (a) Total surface area of carbon = X 10 cm
7 logp
r= 10-8 cm
= nr 2 = -22 xl0-16 cm
2
7
1 1
44 X 107 Slope = - = 2 ⇒ n =-
n 2
- 7- - - = 2 X 1023
22 xl0- 16 Intercept
7
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Surface Chemistry 89
X
Area occupied by single molecules - = 2/0.5 = 4
m
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90 CHEMISTRY
23. (d) Informative = 24 x 10-8 cm2
8
= -- = 8 x 10-12 cm3 2X0.112
1012 ----- X 6 X 1023 = 3 X 1021
0.0821X546
Final side length of each cube= (8 x 1o-12) 113
Specific surface area
=2 x 10-4 cm
3xl021 x0.4xl0- 7 x10- 7
Final surface area = 6 x (2 x 1o-4)2 5
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General Organic
Chemistry
I~ COOH
•
(a) HO ~ COOH (b) H3~ ~ COOH
(c) HOOC ~ COOH (d) NC ~ COOH
2. Which of the following is/are correct order for Ka?
c0
COOH COOH COOH COOH
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92 ===================== CHEMISTRY
~) o $:e>0
~
>
e
N02
0 ~:e>
e
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General Organic Chemistry 93
HN
~
I
H
7. Which of the statements are incorrect?
w
8. Which of the following is/are correct?
~) ¢ a >
0
o
(order ofR.E.)
0
(c) Carbolic acid not react with NaHSO3 but react with Na
Ph
~) l Q > (HOC)
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94 ===================== CHEMISTRY
(;'yo
(d) ~
\
( I ) Integer Answer
11. P = Number of anti-aromatic compound in given list.
CH 0
•
□ @0 0 60
f
Q = No. of resonating structure of SO 42- R= No. ofa-H i n u
OH
@,
Then (P + Q + R + S + T) - 15 is ?
12. How many compounds liberate hydrogen gas on reaction with Na metal?
OH
0 @0 0 0
( I) (2) (3) (4) (5)
HO~OH
COOH
(6)
CH3 - CH3
(7)
HO
o*o 0
(8)
OH
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General Organic Chemistry 95
H0)-1'0
00
( 15) ( 16)
CH3 -CH = 0, CN-, SCN-, Na El\ Cl-, OCN-, NCS-, N3, CH3COO-, C20~-, C202S~-,
(1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11)
08
14.
(12) ( 13)
EB NH2
HO/'-../
R OH ,
✓1
15. How many of the following are more stable than Ph - CHf?
VIII IX
YL ,
EB O co3~
CD3
co
·3
o EB,
X Xl Xll
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96 ===================== CHEMISTRY
16. Number of species which will show amine inversion more comfortably than (ipr)3N:
I
H
17. The compounds which are more acidic than HC = CH.
H
,0 , CH 3 - CaCH,
8
18. Which of the following are better nucleophile than@-~ : in polar aprotic solven?
8
H,N -@--0°, r-, B,-, c1-,F-, @ - s 8 , @ - se , @:o 0
,
@-oH
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General Organic Chemistry 97
EE>
Column-I (Reagent)
(p) +I
Column-II (Product)
•
(A) - NH3
EE>
(B) - PEt
(q) -I
3
..
(C) - 9 C2Hs (r) +R
H (s) -R
(D)
~ Cl
(t) + H
(u) -H
20. Match the columns :
Column-I Column-II
N (p) Carbene
(A)
0~ t:,.
.'
o-◊Ts
(q) N itrene
(B) t:,.
.'
t:,.
(C) CH2CO . (r) Free radical
(i)
Passage-I
Aromatic compounds are those that meet the following criteria :
The structure must be cyclic, containing (4n + 2)n electrons
•
(ii) Each atom in the ring must have p-orbitals.
(iii) Unhybridised p-orbitals/lone pair/ vacant orbital must overlap.
(iv) Structure must be planar.
In anti-aromatic compound (4nn) electron are delocalization but delocalization of TT-electrons over the
ring increases the electronic energy.
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98 ===================== CHEMISTRY
(c)
~
(d)~
(a)
C = C (x) is more reactive towards methylene insertion because it do not involve in aromaticity.
¢
0
(c) o(
D
D
and A are not same at very low temperature.
D D
Passage-II
OH OH OH OH
~OH ~ N02
( i) lSJ (ii) ~
~OH
(v) lSJ (vi)
@lN0 2
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General Organic Chemistry 99
(x) '$
OH OH OH OH
~ COOH O2N ~ N02 /2yN0 2
NO2 NO2
(a) (i) > (ii) > (iii) > (xi) (b) (ii) > (iii) > (i) > (xi)
( C) (ii) > (xi) > (iii) > (i) (d) (ii) > (i) > (iii) > (xi)
OH
24. @ K,:,o, p
(Major)
~
OH
(b) ~
LS(OH
(c) (d)
LOH
lSJ
OH
RESPONSE SHEET
1. ~®@@ 2. ~®@@ 3. ~®@@
4. ~®@@ 5. ~®@@ 6. ~®@@
7. ~®@@ 8. ~®@@ 9. ~@Cs)@
10. ~®@@ 11. 12.
19. IAI 1
8 1 lcl lnl 20. IAI 1
8 1 lcl lnl
21. ~®@@ 22. ~®@@ 23. ~@Cs)@
24. ~®@@
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100 CHEMISTRY
ANSWER KEYS
1. a, b, c 2. a, C 3. a, b, c, d 4. a, b, d 5. a, b, d 6. a, b 7. a, b
8. c, d 9. a, C 10. b, c 11. 10 12. 8 13. 8 14. 9
15. 9 16. 0 17. 12 18. 10 19. A - q; B - q , s; C - q, r; D - p , t, u
20. A - p; B - s; C - p ; D - r 21. a, b , c 22. a, b,c, d 23. d 24. a
,, .
Hints & Solutions : l :
- - - - -0''
1. (a, b , c) (b) More resonance so more R .E.
- I > - OH - I Power. (c) First compound has 4 canonical while
The correct order of -I is second will have only 3 canonical.
(±) (±) (±) (d) First will have 4 canonical while second
- N R 3 > - SR2 > - N H 3 > - N02 > - CN >
will have 3 canonicals.
0 4. (a, b , d)
II (a) HCOOH Ka 17.7 x l0-5
- S03H > - CHO > - C - R > - COOH > -F
Ph- COOH Ka 6.3 X 10-S
> - Cl > - Br > - I > - OR > - OH > - NR.z (b) Due to resonance
> - NHR > - NH2 > - C = CH (d) Squaric acid has 4 same canonical w hile
R - S03H have 3 and R - COOH have 2.
> - @ > - CH = CH2 > -H 0
>o >o
3. (a, b , c, d)
(extent o f
(a) Due to hydrogen interference first
(a) O aromatic compound is not planar.
s N
I
0 behav iour)
.
(b) CF3 is sp3 ,
Q
C
H
F/1 '-F
F
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General Organic Chemistry 101
8. (c, d) 0 0- 0
OH II _ _ I _ 11
Ph
l
0 0
(d) I I
O= S= O ~ O= S=O
Ph II L
0 0
= 5.
Aro Aro
9. (a, c)
(d)CH 3 - CN
HC=CH
PKa = 24.9
PKa = 25
R= u~ cxH= 6.
S = n = 3, p = 2, 2 3 - I + 22 - I = 4 + 2 = 6.
CH 3CN is more acidic is correct. T = All (5)
(a) Frequ ency of inversion depends upon (3 + 5 + 6 + 6 + 5) - 15 = 10.
the energy of square planar transition 12. (8)
state. Which will be less stable in case of 5 R - S03H > R - COOH > Ph - OH > H 2 0
membered ring, so it w ill have less frequency > R - OH > R - C = CH>R -NH 2 >R - H
of inversion.
(b) HOC oc number of carbon. Na start reaction
So (2), (3), (6), (8), (9), (13), (14), (15) will
(c) More conjugation leads to colour in alkenes,
give H+ and will liberate H 2 .
so Ph - (CH= CH)4 - Ph is colourful.
13. (8) Ambidentated Nu
.. ⇒ which have more
10. (b, c)
+ - than one kind of donar sites.
(b)O = C = O ~ O=C - O
2, 3, 6, 7, 11, 12, 13, 14 = 8.
~ -0 - C=O+ 14. (9)
+ e All carbocation in which stability increases can
(c) CH 2 = C = C = CH 2 ~ CH2- C = C-CH2 undergo in rearrangement process multiple times.
11. (10) 15. (9) I, II, V, VI, VIII, IX, X , XI, XII= 9.
P = 3, Q = 5, R = 6, S = 6, T = 5
16.
..
So, total 9 carbocations.
(0) In (ipr) 3N
25 - 15 = 10.
N
P=D C11
N
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102 CHEMISTRY
CH 3CN, ~
0 0
, ~OMe
0 0
,y0 0
0
/',.
----+
0, CHi(CN)2 , CH(CNh , 0 ,@
0
I (±)
N
/'-.H
21. (a, b, c)
H 6ne- aromatic.
(a)~
t
Singlet carbene
(Carbolic acid)
(b) 18ne- cyclic conjugation and no hydrogen
interferance so aromatic.
18. (10) 1, 2, 3, 4, 5, 6, 7, 8 , 11 , 12 are better (c) 14ne- aromatic
nucleophile : (d) 16ne- anti-aromatic.
8 8 8
R - Se > R - S > R - 0 } Nucleophilicity. 22. (a, b , c, d)
19. A- q; B - q, s ; C - q, r; D - p , t, u ; (a) Only conjugation occurs at periphery of
EB molecule.
(A) - N H 3 --> It will show only - I effect not
resonance effect because it does not have any
vacant orbital.
EB
(B) - PEt3 --> - I as well as - M (due to vacant
d orbital)
(C) - 9 C 2H 5 --> - I as well as + M (c) Bond length are different so they are not
H same.
I (d) Cyclic conjugation takes places in benzene
(D) - C- Cl --> + I and Hyperconjugation itself so all are aromatic.
I 23. (d)
CH3
due to C - H bond and reverse hyperconjugation
due to C - Cl bond.
20. A - p ; B - s; C - p ; D - r;
~
Carbene
0 - I 24.
+ OTs
OH
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Isomerism
M(® 1
H Me •
N
H,,,A,,Me
Me H
H* OH H* OH
(b) H OH HO H
H OH H OH
Me Me
Me Me
H Cl Br H
(c) (d)
Br H CI H
= Me Me
3. Which of the following is/are correct?
(a) N-methylethanamine exist as non-isolable racemic mixture.
(b) N-methylethanamine react with excess at DCl and give configurational enantiomers.
(c) Two confo rmational isomers of butane have equal energy and they are chiral.
(d) Penta-2,3-diene exist in optically active isomeric form.
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104 ===================== CHEMISTRY
(d) Twistane
Q R2 OH
I
OH
I
(a)
N R, ~ rN _;R3 (b)
R~i~R HOOC( / i ~ H H( / J ~COOH
=
I
R2
3
0 Me Me
(c)
Me( /
.. e
C
1~C2H 5 H 5C? " Me
.. e
C
1~ (d)
4"-H
<r/H&
Q
6.
H H
The compounds which can show racemisation under mild basic condition is/are?
0
Me Me
0
(a)
0
ft~ 0
(b) (c)
~
,/✓
,,,
O
(d)
Me . Me Me Et
7. If x = Total number of chiral steremsomer of 1,2,3 ,4,5,6-hexachloro cyclohexane.
If y = Total number of a chiral stereoisomer of 1,2,3 ,4-tetra chloro cyclobutane.
(a) x + y = 6 (b) x + y = 8 (c) I x - y I = 2 (d) lx- y l=3
8. The conformer in which gauche form is m ore stable than anti
(a) F - CH 2 - CH 2 - F
~) F - CH 2 - CH 2 - CH3
$
(c) F - CH 2 - CH 2 - NH3
(d) HOOC - CH 2 - CH2 - COOH in NaHCO3 solution.
9. The compounds which are meso?
Cl
OH OH
J
u
C~ f>CI
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Isomerism 105
(a)
Me
H
>=c = C=
/Me
C',_
H
(b) 0
Br H00C Br
/0~0~
(c) (d) ~
H00C l N02
( I ) Integer Answer
11.
12.
Total no. of cyclic structural isomer possible with formula C 6H 10 .
Find out number of compound those have ' R' configuration from following.
CH 21
I
HytyH
•
0HC j
~
- { H
CH20H 0 H~Br
H
Br
I
13. Total number of compound having POS are :
H_=f=CH
3 Br
Cl H
H Br
C
CH3
FAF
u
H H
(Uans-COT)
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106 CHEMISTRY
F
14. Total number of optically active isomers possible for this compound.
COOR
CH = CH
I
CH
Br N02 II
C
Me-NH
. is( 1.
0
; - CH = CH
s~
"o
MH
I
oa
Et
17. The compounds in which enol form is more stable than keto form.
0 0
0
(I)
6
(2)
6a(3) (4)
0
(5)
0
00
A A OEt
(6)
00
AA
(7)
0 0 0 0 0
~ ~
II
0 2N - CH2 - C - Me
Ph
0 (8) (9) (10) ( 11)
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Isomerism 107
0 0 0
Ph ~
~ 0
otf° HNC
(A)
Match the Column-I with Column-II :
Column-I
(p) 2
Column-II
•
0
II
MeO -P
~
OMe
(B) NH2 (q) 4
~0
MeO-x~k _JV
OMe
(C) (r) 6
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108 ===================== CHEMISTRY
(D) OH (s) 8
c;6 0
20. Match the columns :
Column-I Column-II C olumn-II
(A) (p) P OS (w) 2
0
(
(B) ( q) Optically active (x) 8
Cl
(C) (r) Show geom etrical isomerism (y) 6
11
~
(D) 0 (s) cos (z) Zero
00 0
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Isomerism ========================= 109
H Cl
2 1.
Cl H
(a) It is optically inactive due to POS (b) It is optically inactive due to COS
(c) Itisoptically inactive due toAAOS (d) All (a), (b)and(c)
22 Which of the following compound are optically inactive?
0
//
(a)
Me
(c) oo (d)oo
Passage-II
Me
NH
Cyclohexane exist in many conformations at room temperature by flipping process with frequency of
10 8 per second. Considering this, answer the following questions.
23. Number of carbon in one plne in half chair form?
(a) 2 (b) 3 (c) 4 (d) 5
24. cis-1 ,4-ditertbutyl cyclohexane exist in which conformation?
(a) Chair (b) Boat (c) Twisted Boat (d) Half Chair
RESPONSE SHEET
1. ~®@@ 2. ~®@@ 3. ~®@@
4. ~®@@ 5. ~®@@ 6. ~®@@
7. ~®@@ 8. ~®@@ 9. ~@Cs)@
10. ~®@@ 11. 12.
19. IAI 1
8 1 lcl lnl 20. IAI 1
8 1 lcl lnl
21. ~®@@ 22. ~®@@ 23. ~@Cs)@
24. ~®@@
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110 ===================== CHEMISTRY
ANSWER KEYS
1. C 2. a 3. a, b, c, d 4. b,c, d 5. a,c 6. a, d 7. a,c
8. a, b, c 9. b, c 10. a, b, c, d 11. 54 12. 4 13. 9 14. 4
15. n = l + 1 + 1 + 1 + 5 = 9. 16. 9 17. 8 18. 6
19. A - q; B - p; C - s ; D - s ; 20. A - q, r,q; B-p , r,s, w; C - q,r,x; D- q,z; 21. C
H
I
(a) 0~:
Me
" /
NEE>
Et
are enantiomers.
(c) Gauche fom1 of butane are chiral.
I
D +
0 Q
H
;;,
0
D
,....Me
⇒
H/
(d)
CH3'' '-
C = C = C"
~
.,,,,, CH3
~ H
I CH/11,,.
H 'V"
·c = C = C
/ CH3
'-.H
Me
Racemic
(d) (£) OH
(d)
4. (b, c, d) Option (a) contains POS, so optically
inactive.
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Isomerism 11 1
Chiral stereoisomer = 2 (d + l)
~
~
Cl ) = = (Cl C
l)==(Cl
Cl Cl Cl Cl
Racemic
POS POS
7. (a, c)
Cl
Cl
Cl
Cl ~C l
CI
= Cl µ :•''"C l
Cl :7·•' 'Cl
''1 Cl ~, , , . ~C l
Cl 'I/c l
Cl CI CI Cl POS POS
Achiral = 4
Cl Cl
12 -4 1= 2
Achi ral POS
(POS) l x + y l= 2 +4= 6
Cl Cl Hence, (a) and (c) are correct.
8. (a, b, c)
Cl Cl Cl
H F F
(a) ~ (cr - cr*) hyperconjuation.
Cl CI Cl f~H
H
Cl Cl
So, Gauche is more stable.
POS POS (b) Due to dipole-induced dipole force of
Cl Cl attraction in gauche form.
= =
ClyYCI Ct ) ? =.,,,,\ Cl
(c) Due to ion-dipole attraction in gauche form.
coo-
Cl ~CI
Cl ·,,,I/ C I (d) H:$:H in basic medium there will
CI Cl H _H
coo
POS cos
be no H.B .
Cl Cl
9. (b, c) Meso compounds are the compounds
=
Clxx:=
.,, ,,\ Cl
Cl Cl which contains chiral centre and are optically
inactive due to internal cancellation of plane
polarised light.
Cl :. Cl So, (b, c) are correct.
10. (a, b , c, d)
Cl Cl
(a) First and last are in same plane, so distance
(O.A.) cos
can change.
(d &£)
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112
~
(c) Distance between Br and Br can change. L
The given molecule is cis.
(d) First and third ring lies in plane so distance
between O and O can change. Y ~ ~
[T
A A .b.
11. (54)
A
v CD \_J
h A 6
0
1 2 ._ (4)ApplyCIPRule.
LJ 13 (9)The following compound will show POS.
66er-~d 1
ctdcrcsrczr I
<t
d- a- c::( D( c(
F~
!
F
c( cz(~p
P;s(E£
£~~SE
~~~~
F
~ ~ ~2(A
A p,<J [>---<]
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Isomerism 113
0 .1.
~ ~
~ O.A.
~
n = 4; Stereoisomer = 2.
~
~ ~ O.A. Because all are fixed.
~ otio
/ H .,
(C) Excocyclic C = C can show G.I.
(D)
r··············..
d ------- ,,,
(1 4) == 100% enol
0 0 O- H- O
AA~AA Optical active because it is having no symmetry.
(76% enol)
W WW.JEEBOOKS.INI
114 CHEMISTRY
21. ( c) AAOS is defined as consider an axis, 22. (c)
rotate the molecule around it by an an gle
8 and take mirror image around that
axis (mirror plane should be 1- to axis)
the new molecule must be identical to It contain POS so it is optically inactive.
DO H
RESPONSE SHEET
1. ~®@@ 2. ~®@@ 3. ~®@@
4. ~®@@ 5. ~®@@ 6. ~®@@
7. ~®@@ 8. ~®@@ 9. ~@Cs)@
10. ~®@@ 11. 12.
19. IAI 1
8 1 lcl lnl 20. IAI 1
8 1 lcl lnl
21. ~®@@ 22. ~®@@ 23. ~@Cs)@
24. ~®@@
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Hydrocarbons and
Halogen Containing
Compounds
(a) ~
BH3 / THF
(b) ~
BH3 / THF
•
NH2CI X2
Hg(OAc)i I H2O
(1 )9-BBN / O
J
(c) ~ (d) ~ )
NaBH4
(c) & sr
3. In which reaction C = C is more reactive than C = C ?
(a) Towards dil. H 2 SO4
(b) In ozonolysis
(c) In catalytic hydrogenation
HCI
(d) HC=C - CH =CH z --➔
(a) l (b)
R OH
(c)
HOA NH2
(d)
o;
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116 CHEMISTRY
~
5. HCl / t:-.
I mol.
possible products
(a)
~Cl Cl
(b)
¢Cl
(c)
Qc1 (d)
6
X
2HX I .
6. CH 3 - C= CH CH3 - C - CH3 1s true for
I
X
(a) X = F (b) X = Cl (c) X = Br (d) X = I
7. In w hich of the follow ing the rate of SN 1 and SN2 follows the same order ?
0
(c) ~ CI > ~ Cl (d) ~ Cl > ~ Cl
8. Which will be anti elimination?
(a)
H
Cl-+-H
Me
----t--
Br
Me
Zn / dust
,t,;.
(b)
Hi=!
H
CH 3
I
Self
~
/";.
(d) All
Br
9. - c=c"""124- ~ ) (P)
( I eq.)
Correct statements about product?
Br Br
(a) Pis ~
Br
(b) Pis
Br
~
( c) Alkene w ill be cis (d) Alkene w ill be trans.
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Hydrocarbons & Halogen Containing Compounds 117
(c) □ (d)
( I ) Integer Answer
11.
0 Cl2
hv
~
: CH2
~
: CH2
(c) (R) (d) (S)
Singlet Triplet
: CH2
~
(e) (T) (f) ~ B , Cone. NaOH (U)
Triplet 35°c
H 2 / Pd-BaSO4 Na / liq. NH 3
(4) (6)
Br
15.
OC Cl
What will be the D.U. of P?
D.E.
Na
p
CH3 H
~ -,,~ BH3 / THF HBr
(c) ~
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118 CHEMISTRY
Me H
(e)
~ 0
CH3 OH 8
Traces
(f)
0 Br2 / CCl4
(g)
00 OH
Br2 / CCl4
(h)
co Br2
CC I )
4
(i)
Q
CH3
1/
H
li
!!,.
(j) @r'
0
Br 2
hv
)
(k)
0
)l__,,,
(m) Sucrose
KCN
H30EB
6
(1)
LAH
18. @2mol
+ Cl3C - CHO Cone. H 2SO4
!!,. (P)
F
OH 8
!!,.
~
(B) !!,. ., (q) Sytzeff elimination
0 - C - SMe
II
s
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Hydrocarbons & Halogen Containing Compounds 119
(5-+◊K+ /';. .
20.
tY ale. KOH.
Column-I Column-II
(A) (p) Meso
6 HCI
~
M.
aJ0f
er
(B) (q) Racemic mixture
Cold KMnO 4 ;
Cf,,,
u
HCI
~ Major
rc:nr an BH, ,s
Passage-I
e(octrnpluhc spec;e, wh;cohOha
•
ve only 6e- and solvated by a solvent THF
H 3B
It is a syn addition reaction that takes place with alkene and alkyne. Answer the following questions.
2 1. During mechanism which of the intermediates is/are not obtained during this reaction?
>=
BH3 / THF
';n
H OH
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120 CHEMISTRY
0 - 0 - ----<
I
(b) _,,,,.B......_
;:0 - 0 0 - 0~
22. Which of the following can be used to convert this reactant into product?
0
? II
CH 3 - C =CH ~ CH 3 - CH 2 - CH
Passage-II
Conjugated diene (4nrre-) reacts with unsaturated (2rre-) in presence of heat to produce six membered
ring. It is called Diels-Alder (4 + 2) addition.
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Hydrocarbons & Halogen Containing Compounds 121
(a) (b)
CN
(a) ~ (b) Q
I
(c) 0 (d) ~ ~
RESPONSE SHEET
1. ~®@@ 2. ~®@@ 3. ~®@@
4. ~®@@ 5. ~®@@ 6. ~®@@
7. ~®@@ 8. ~®@@ 9. ~@Cs)@
10. ~®@@ 11. 12.
19. IAI 1
8 1 lcl lnl 20. IAI 1
8 1 lcl lnl
21. ~®@@ 22. ~®@@ 23. ~@Cs)@
24. ~®@@
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122 CHEMISTRY
ANSWER KEYS
1. (a, b, d) 2. (c, d) 3. (b, d) 4. (b, d) 5. (a, b, c) 6. (a, b, c, d) 7. (a, b, c)
8. (a, b) 9. (b, d) 10. (b, c) 11. ( 12) 12. (40 .54) 13. ( 17) 14. (5)
15. (7) 16. (6) 17. (8) 18. (8) 19. A - q ; B - p , r; C - s,p; D - q , s;
20. A - s; B - p , t; C - s, t; D - t; 21. (b) 22. (a, b, c) 23. (a) 24. (c)
_. \ ..._
\ I I \ I I
~
BHJ / THF
NH2Cl
)
h NH2 H
4.
other hence ring will expand.
(b, d) Will give m ore stable C9 .
»
H 5. (a, b , c)
~ BHJ / THF )
X2
~
9 BBN / 0 0
H 20 2 / 0H
h OH H
9 - BBN ⇒ A -H >~
(Major)
HCI
b.
2. (c, d)
!
(d)
HC = C-CH = CH2
(due to
hindrance)
Q,
(Minor)
~
Q
~ ) 2~
+
H
I® 3 5 \~
~
Chloroprene
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Hydrocarbons & Halogen Containing Compounds 123
{-I >+ M}
Rate of Si
CH 3 - Cl 200 Br~Br
10. (b,c)
MeO/"'-...CI 720
~ Cl 200
Cl
Cl 2 I
~~~ + ~
Cl (2)
+~
Cl
Resonance stabilized T.S. (4)
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124 CHEMISTRY
[]-~: [J'cid-ci
14. (5)
(7)0: ~
l }=]
15.
c(C
(4) Cl (2)
3 mol.
D.U. = 7.
= 8 products 16. (6) (a), (e), (f), (i), (j), (k) will
mixture. prntluce racemic
c1i
II ~
hv II \
Cl
I product
(f)
( l·''~Br
11. (12)
0 Br2
½
~C
IQ Q:c1sfyci
CCI )
4
Cl Cl
Br
enantiomer
13. (17)=(P)
(U) 2 = 6, (Q) = 1, (R) = 2, (S) = 3, (T) = 3, (P)-0 a-H = 2
(Q) =
c5
a-H = 6
6+1+2+3+3+2 =1 7
(b) . 18. (8)
: CH2 : Cl
Singlet ) \ ~
; / (OnlyMeso) (1) I Cl
I CI -C-CH
!
I
(c)
: CH2
Singlet ) ~ ~
\___ I (2)
Cl
1-H,0
Cl
Racemic C\ 0--- c 1
(e) CI -C-CH ~
V ~ I~
Cl / '@-c 1
\=.I . CH2
Triplet +
3
( )
D.U = 8.
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Hydrocarbons & Halogen Containing Compounds 125
H H H
u A+u
~
OH OH ~
~
,...
~ ..,;'
~OH
(C)
Et
@ - cH = CH - CH3
/"J?.
"=l·•I/// H ---+
HCI
(Sytzeff of Product)
~ ~~
Optically
a
Inactive
+ MeSH + SO2
O-C-SMe
II
0
Hg (OAC)2 I 8i0
(D)
(C)
Bulky base do
Hoffmann elimination
6 21.
,
(b)
/ ott, , rn,
c-- c '\._-3times
- -R B
R
I tt -~ H
H- 0 - 0
e
/ / ~
Cl
OR R R
(D) ~ H ale. KOH
I 2 times I eI
B ~ R- B - 0 - 0 - H
(E2+ sytzefl) OR
/B'\.
OR ✓ 'oR c!JV
20. A - s; B - p , t; C - s, t; D - t;
Hence, option (b) is not formed.
(A)
22. (a, b , c)
To follow anti-mackownicov we use hydrobo-
ration oxidation. So all three (a, b, c) are cor-
rect.
4 products
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126 CHEMISTRY
Me Me Me Me aromatic behaviour.
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Alcohol, Phenols,
Ether, Aldehyde &
Ketones
~ MCQs with One or More than One Option Correct
1. W hich of the following can not show Aldol condensation (self)? •
6
CHO
0
(a)
OH
'8'
~ OH
(b) 06
II
Ph-CH 2 -C-CH 3 (c)
0
$
CHO
/ N "-.
4. Which of the following reaction will produce Ph - CHO as a product?
(b) @J HCl+CO
H
CHO
5.
6 ~ r,
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128 CHEMISTRY
OH
0
(,)@ Fe2+
(b)@r) ~
Li
0
II
0 - C- R
(c)@ ~
HBr
Cone.
(c) ~ ~
3
(d) A Cone. H2S04
Li
0
8. Identify the reactions in which correct product is mentioned?
0 0 OH
(c)@ 0
=O==O= --
0
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Alcohol, Phenol, Ether, Aldehyde & Ketones 129
0 0
II
(d) Ph -CH= CH - C-CH =CH-Ph + CH 2 (COOEt)i
Phf)Ph
EtOOC COOEt
9. Identify the intermediate products during the entire course of following reactions.
OH
0 =Q 0
( I) CH3MgBr
(2) Hp
(3) OH
6
/ti
isl
(,) D
OH OH 0
0
0
(b) X
AAo (d) 6 0
A Br2
oT-f3 ) (P) + (Q)
I Br2
CH COOH) (R)
3
Correct options is/are?
0 0
(a) (P) = Ao0 (b) (Q) = CHBr3 (c) (R) =~ (d) None of these
Br
( I ) Integer Answer
11. Number of moles ofCH4 obtained when 1 mol of the given compound reacts with excess ofCH 3MgBr.
SH OH
•
OH
CN OH
12. Which will give +ve Br2 I H 2 0 test? Calculate the number of compounds.
~ CH3 -CeCH O @ 6 D
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130 CHEMISTRY
0
0 0
13.
CH 3 - CHO HCHO
A Glucose
Degree ofunsaturation of the product + No. ofN atom in the product will be equal to?
Fructose
NH3+HCHO p
0
Ph Ph
Glycerol
H
(±)
p
_x_CH_I)➔
15.
CX O:rsrO....,__Ph
0
The value of x = ?
0
/ Et
16. Number of compounds which can not show +ve Iodoform test?
HCHO, Me - CHO, Et - CHO, Et - OH, Cl3C - CHO, Me - COOH, Me - COCl, ipr-1, Et-I
OH O O O O O 0
OH
17. Number of compound which can give the Tollen's Test.
OH
Ph/ n
.,,l_ _,, , CH3
0
Glucose Fructose Ph- NH-OH HCOOH
0
18.
CH 3 - CHO HCHO
~
OH
OH
AA
OH OH
+uu 0
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Alcohol, Phenol, Ether, Aldehyde & Ketones 13 1
OH OH
~K KOH
OH OH HO OH HO ~H
~ NH 2
~ OH
U oH
(B) (q)
~0
OH
COOH
H$ / KMnO 4 / 25°C
(C)
A0
(r)
n CHO OH
~
(i-pro) 3Al /
0 CHO
(D) (s) OH
~
C,03 / @ / HCI
N
O OH
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132 ===================== CHEMISTRY
(B)
60
HCN
traces of KOH
A
LAH
B
NaN02
HCI
C
(C)
6 NH20H
A ~B
HGl
~
HGl
CH3 ~ A
OH OH
(t) Ring expansion takes place.
[CJ
[A] ----+ + ve Victor Mayer Test (Red)
I J>
.___ _Li_ _ _
) W (maj or)
2 1. W is
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Alcohol, Phenol, Ether, Aldehyde & Ketones 133
~ ~
OH
(a) ( O) (b) ( OH Conc. H3P04
C0
Cone. HiS04
HO O OH
OH OH
LoNoH
Ph Ph
OH
OH
QA
RESPONSE SHEET
1. ~®@@ 2. ~®@@ 3. ~®@@
4. ~®@@ 5. ~®@@ 6. ~®@@
7. ~®@@ 8. ~®@@ 9. ~@Cs)@
10. ~®@@ 11. 12.
19. IAI 1
8 1 lcl lnl 20. IAI 1
8 1 lcl lnl
21. ~®@@ 22. ~®@@ 23. ~@Cs)@
24. ~®@@
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134 CHEMISTRY
ANSWER KEYS
1. a, b,c, d 2. a, C 3. b, d 4. a, b,c, d 5. a, b, c 6. a, b, c, d
7. a, b, c, d 8. a, b,c, d 9. a, b, c 10. a, b, c 11. 11 12. 10
13. 7 14. 4 15. 4 16. 7 17. 9 18. 8
19. A - q; B - p; C - s; D - r 20. A - p , q, s, t; B - p , t; C - p , q, s; D - p, q, s, t 21. d
22. a 23. b 24. a, b,c
.. . ..
\ I I \ I I
. \
Hints & Solutions :
.I .:
l,g..__ __
-----·
1. (a, b , c, d)
(a) 0 O~- OH 0
JJ.~- l~OH
~ ~.fl_ ~ e~
H+!
CH3 - CH2 - COOH
(c) 0- CHO ~
t:,.
No condensation
possible due to
OH
I -
1-aH Ph - CI3 ~ Ph - C - OH + 31
I (No iodoform)
OH
(d) @ - CHO
0
: - @ - coo- !-Hp
Ph - COOH
+@ - cH2 - 0H 0 0
2. (a, c)
(c) ,,Jl--, A o
U o1-1- ¼ 2-+ 0- _+ CHI
3
(a)uA
0 0
r2 10H-
CHCI3 + Hcoo-
0 Chloroform
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Alcohol, Phenol, Ether, Aldehyde & Ketones 135
3. (b, d) Exception of cannizaro reaction (b) Ph has more migrating power than 3°.
e
(a)
Me
Me
'\. ®
/N ==0=1 _
O
C- H
6.
(c) R.E. is also known as bond shift.
(a, b , c, d)
OH
(c) Cl -C -
Cl--H- 0
I
I
C---H-0
I
C- H
I
@
(Fenton's reagent)
4. (a, b , c, d)
0
CrOzClz
II
Ph -C- H
CSz
(Eta.rd reaction)
HC l+CO
AICl3
5. (a, b, c)
H 7. (a, b , c, d)
+
OH2
--r-OH
V'I
- H20 )
(a)yy
OH OH
-0-
0
I
ti -0-
s
~ NH
~3~
/ ti-) -CJ-
N
I
So, option (a) is correct. H
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136 CH EMISTRY
08 oH
(Mesitylene)
CJ-f b-()
o 11- I o
--4
CN H
8. (a, b , c, d)
(a)
~ -0-.;>- R
'-, c- f~'n
c~ ,--./,
0
ow
1:,
3
HN0 Oxidation takes place
o,-, 0 o= O = Oo
~ ~ ~ g - OH OH OH
0 ~
(b)G 0 CHO
KCN
9. (a, b , c)
OH
CJ-b:e
o I O~
~
::~~' HO~
Add1t1on ~
CN
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Alcohol, Phenol, Ether, Aldehyde & Ketones 137
HO><:::¥ ~:;;:ii Do D
H 20
Br2
H20
("/Br
OH
D OH @@ Br2
H 20
X
10. (a, b , c)
Br
In bas ic medium whole reaction goes to
completion.
Br2
0 @rs@ Br2
H 20
ow ~ LI
oe + CHBr3 Br
Br2
R -CHO R -COOH
H 20
A CH2Br
(Major)
N atom = 4, ; D.U. = 3 3 + 4 = (7)
(I) R- SH
11. (11 ) RMgX R- H
(2) R-COOH
(3) Ph - OH
Ph
(4) R- OH
0 ~
E~~ ~ ~
4mol.
AH
0 14_ (4) A
X + ;
; OH(a)
OQ O
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138 CHEMISTRY
,
! 0 0 \
Ph
)<Et
~
18. (8)ForHIO4
-
'
CH + ' CH -
1 i I
OH OH (syn)
''
- CH --i- CH -
I i I
OH NH2
' ' .
- CH --i- C- & - c + c-
1 i II 11 i II
OH 0 0 0
Total mole = 4
19. A-q;B-p;C-s;D-r;
16. (7)Me-CHO
0 (1) Cult. only oxidise 1° OH, 2° Hand eliminate
II
Me-C-COOH 3° OH.
OH (4)PCC
0 0
~
PCC
Et-I 1° OH Aldehyde
6 6
0 HO CN
(3)R-CHO
(a) HCN LAH
(4)HCOOH
(7) Fructose
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Alcohol, Phenol, Ether, Aldehyde & Ketones 139
OH
0
6 -H
+
0 2,4 DNP
+ve Test Voilet Complex
[(Ph - 0)3- Fe ]
3+
(B)
(b) 6 60
NH20H
N-OH
H+/ t:,.
Backrnann
CH~
~/
"'1,IN,OH
CH\RTR)
~;o
D ~· CH = N - CH3
6 :~: ~:~
0 \.::}_; (cis+ trans)
(c) a~
...______,,,,,
H o:,
A Idol
OH
Cone. H 2 SO4
23. (b) t1
(
OH
2 mol I r-\ r-\
~HO O OH
Ph P0h Me OH
- H,~ ~ .Ec4 <B
OH Me
NaNO2
............................
HCI
-H· LOO
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140 CHEMISTRY
~OH ~OH
(d)u
u (a)~ Arn
6
OH
Ph
(b) Allylie
c\
Et)
-OH
Et)
(c) /'... Benzylic
Correct Ph
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Carboxylic Acids & its
Derivatives and Nitrogen
Containing Compounds
N0 2
III.
ex OH
OH
+ HI (excess) ~
(l)AgN02
<±>
(2) Fe / H
(C)
Out of A, B, C and D the product(s) which can show hoffmann mustard oil test is/are
(a) B and D (b) Only D
(c) A, B and D (d) Only C
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142 ===================== CHEMISTRY
(a) /4c-t~
NH
(I ) NaOI-1
(2) I-ICI ) (b) 0 hot
(d) ~
4. Which of the following are correct?
(a) Rate of esterification for alcohol CH 3 - OH > 1° > 2° > 3°
(b) rate of esterification for carboxylic acid CH 3 - COOH > 1° > 2° > 3°
0
11 1s
5. R- C-OH+ R '-OH cone. H2S04 >
6
Products obtained
0 0
II 11 18
(a) R -C- O - R' (b) R -C- O- R'
18 18
0 0
II 11 18
(c) R -C- O - R' (d) R -C- O- R'
0
II 18 H EB
6. Me 3 C-C- OH + Me - OH--➔
0 0
11 18 II
(a) Me 3 C-C- O - Me (b) Me 3C-C- O - Me
(d) Me C- O - Me
7. Which of the following ester can show Claisen condensation?
0 0
(a)
)-
II
C- OEt (b)
+ II
C- OEt (c)
~ OEt
II
0
(d) Me-COOEt
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Carboxylic Acids & its Derivatives & NCMP 143
(a) n OAc
OAc
_ t,_
0
II 0
C-0-Me
~QPh
(b) lSJ
0
~II
~ C-Me
OH (3) Me-I
(4) t,
(a)
$ (b) $NH2
NH2
OH
(c)
$CH 3
(d) $OH
0
II LAH
10. CH3 - C - NH2 (I mo!)
X
I LiAID4
) y
(a) X = CH3 - CH = NH (b) X=CH3 -CH=O
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144 CHEMISTRY
( I ) Integer Answer
11. Number of compound which on decarboxylation produces racemic mixture.
Me
•
HOOC - + - COOH
H -----t-- CH 3
Me
P OOH
COOH
Me
A
HOOC ~ COOH --
t:..--+
H Me Me
P OOH
COOH
A
a COOH
Me Me COOH
o:
0
COOH II
F3C - C - CH2 - COOH
(±)
COOH
I t:.. )
t:..
0
II ./ LAH LAH )
(c) ............... N ,, (d) @ - N02
" N02
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Carboxylic Acids & its Derivatives & NCMP 145
(g)
i NO
0
2
(h)
H '-..
CH /
3
0
NaBH3CN
C = NH - - - -
II II ( l ) PCI5
(i) R -C-NH2 (j) R- C - NH - OH - - - +
(2) 01.f / ~
(3) H$
0
CH3CI II ( I) NH3
(k) NH3 excess (1) R- C- CI
(2) LAH
~ HO© 3
(m ) ~ (N-R- -
0
13. Total number of compound more basic than aniline.
cS- ( I)
c$)_
(2)
$$ (3)
OCH3
(4)
-.........✓
N
~
(5)
CH,
@ (6)
e s r - CONH 2
(7)
$ C- H
II cS-NH 2
cS-O
H
0
(8) (9) ( 10)
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146 CHEMISTRY
l ~
Ph - - Ph
r&C
N
( 11 )
Cl
(12)
@( 13)
NH
NH2/
II
C
( 15)
'-... NH2
c5 (16)
~ NH2
14. Number of carboxylic acid that are more acidic than Ph-COOH.
COOH
COOH COOH
@rN0 2
®-NO, $
( I) (2)
COOH
COOH
@rCH, @rNH COOH
$ CH3
(6)
2
(4) (5)
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Carboxylic Acids & its Derivatives & NCMP 147
COOH COOH
$ $
COOH
(9)
S03H
( 10)
COOH
I
COOH
( 11 )
HCOOH
( 12)
( COOH COOH
Me -COOH
COOH HOOC f
( 13) ( 14) ( 15)
15. r\.._L
~0-S
-
II
Me
0
II
-<>-
! O-S-0----r-U
II Me -
0
II ___f__r\
0 H20/Warrn 0
(P)
Total number of product obtained in above reaction.
16. How many of the following amines will undergo diazotisation.
p - toluidine, m- chloroaniline,
(V) (VI)
17. What is the number of isomer with pyridine nucleus possible for compound having M.F. = C 7 H9 N?
0
1. Br2 (1 mol)/CCl4 1. CHr I (excess)
18. A----- B
2. (CH3)iNH 2. AgOH / I'!. (major)
(excess)
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148 CHEMISTRY
dil. H,S0 4 _
/',.
-
(B) 0 (q) Product contains CONH2 group
(C)
6 (!) KCN / H2 S0 4
0
6
NC+=(CN CN
/',.
II
HONO.
/',.
8
s03
OH
(D)
N02
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Carboxylic Acids & its Derivatives & NCMP 149
0 -~-~-H
0 0
Passage-I
(1) 0: P,
LiAIH4
•
0 (2) H
I- - - - ~ ) P3
RedP + HI
2 1. P 1 is
(a)
0~
~
OH 0
(b) O - t H- ~- H
0
OH
(c) O - bH -COOH
0
0
(d) O - ~- COOH
0
22.
Passage-II
0
0 0
+ B, 2 + KOH ~ P, + P2
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150 CHEMISTRY
+ COOH
(1) H IB
24 P.2
· (2) CaO / Li
r----f'o
(b) L_j
(d) L
RESPONSE SHEET
1. Ci)@@@ 2. Ci)@@@ 3. Ci)@@@
4. Ci)@@@ 5. Ci)@@@ 6. Ci)@@@
7. Ci)@@@ 8. Ci)@@@ 9. Ci)@@@
10. Ci)@@@ 11. 12.
19. IAI 1
8 1 lcl lnl 20. IAI 1
8 1 lcl lnl
21. Ci)@@@ 22. Ci)@@@ 23. Ci)@@@
24. Ci)@@@
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Carboxylic Acids & its Derivatives & NCMP 15 1
ANSWER KEYS
1. a, b , c, d 2. d 3. a,c 4. a, b, c 5. a, c 6. C 7. c, d
8. a, b , c, d 9. a, b, d 10. a,c 11. 3 12. 9 13. 13 14. 13
15. 3 16. 5 17. 9 18. 0 19. A - p; B - q , s; C - p , r; D - p;
20. A - r, s; B - q; C - p , r; D - p , r, s; 21. C 22. a, b , d 23. a, b, c 24. a
.. .
\ I I \ I I
____......,,,. .
_ \ .,_
• , u __ _ __ Hints & Solutions : I :
Me Cl Cl Cl 0
(a) N d N
I
O
NaO H II
-----+ Me-C-C-C-0
II I II
e
N
I
Cl
I
H NH2
2. (d)
Me - C = C - Coo-
CH2NHCH 3
(B)
HCOOH
4. (a, b , c)
1
Rate of esterification oc - - - - - -
Steric hindrance
5. (a, c)
,--4'0 ,-----(NH2 + N 0 08
u +u VITTI R-
II
C-
!~
OH ~
I ..(r)
R- C= O- H
NH ! ·, s
~□□ (D)
OH
I
R- C= O
18
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152 CHEMISTRY
01 8 018 (c)
II -Hp II 0 0
R - C - (6Hl+R' - OIH] ~ R - C - 0 - R'
II
- - ester
@- C - OH
MeLi
@- II C - 0 - Li
e +
6. (c)
0
II 8
+
Me3C- C-OH--➔ Me3C-
0
II
C-OH2
+ ! Me-Li
!-H 0 2
8
0 L/
Me3C-C = o+ @- I ? - 0 Li
e +
!-eo Me
I Me3C-6- Mel _M_e_-6_
8H-Me3CGl !H 0+ 3
OH
This is known as A Ac' mechanism.
0
II
@-~-Me
0 - C - Me (d) Pyrolysis of Xanthate
Me - C - 0
II
*0-C
-Me II
O
A D
(Pyrolysis of ester
is Hoffmann)
~OH
( l)Na
~0 - C- S
e
II
s
0 lMe - I
(b)
?-~
0 - C - S - Me
II
s
Pyrolysis follows Hoffmann elimination.
9. (a, b , d)
0
OH 0
A Product
$ OH
¢
0
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Carboxylic Acids & its Derivatives & NCMP 153
OH 0 0 12. (9)
¢ ¢
0
$ H
+
[OJ
(a) ~ NH
2
LAH
CH3 - CH2 - NH2
NH
NH
0
0
(e) O - N02
LAH
o-N
H 2
NH2
¢ ¢
NH
[OJ
10. (a, c)
~ NO2
Me
11. (3)HOOC+ COOH ~
H
0
HOOC+
Me
H + H + COOH
Me II
(i) R - C- NH 2 -:~~k~ R - CH2 - NH 2
H H (j)
OCOOH-40
0 0
(2)
R-
0
II
C- NH -
PCl5
OH -----. R -
0
II
C- NH -
l OHe
Cl
o: COOH 0
11 11 . :3
No reaction R- C- N- Cl
(±)
COOH
l-er
~~D
l'vcooH
ID IR - NH I~OH-/11 0 -- C -- N -
2 R~ R-
0
11,r:N:.
C-
N02 N02 10 ~
(±)
(racemic)
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154 CHEMISTRY
! LAH
Me 20 _1.
same
Me
~/
N- R Hp•, ( o YCOOH+ R - NH,
~ COOH 1°
@:L@r'@ @X
0
13. (13)
(2), (3), (4), (5), (6), (10), (14), (15), (16), (17),
@l '@_~ @r '@'
(1 8), (19), (20). 18. (0)
14. (13)
COOH COOH
~
l2)
G > Ao
l2)
(due to ortho effect)
*
(G NH 2 exception)
(I
17.7 x 10
-5 I -5
6.3 x 10
I
1.7 x 10-
5
(K.)
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Carboxylic Acids & its Derivatives & NCMP 155
19. A- p ; B - q, s; C - p , r; D - p ;
0
rlo Ho+ rlo
6 Nc-t-------\CN~
CN
ooc-t-------\COOH
COOH
µ
(C)
(B) 0
! HCN ~ + co,
OH CN HOOC
XONHz
V
+E-H_2_0..,.
oHe
2-
6 ++ OH NH 2
HONO
20. A - r , s; B - q ; C - p , r; D - p , r, s;
Compound in (A) will not show lassaigne test as it does not contains carbon atom SO, in sodium fusion
extract 'N' is not available as NaCN .
In (B) all 'S' present in it will be present as NaSCN.
0 0 OH
0 -~-~-H
0
( I) OH
(2) H
+ O
0
- tH -COOH
Pi ! LAH
OH
O - 6H -CH2 - 0H
0
! Red P/Hl
0\
'/
0
\ - COOH + - - -
KMnO4
! sOCI2
0
O - ~ - CI O - CHO
0 0
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156 CHEMISTRY
2 1. (c)
22. (a, b , d)
1,3-Diketone can show iodoform.
1,,...c1 _ M
_g_ I _,... Mgct
~ ether ~
H+ COOR
p 2 ~ HOOC ~
!
C
Cao
coo- 2+ 1:i
COO- Ca ~ CaCO 3 +
6
o
23. (a, b , c)
24. (a)
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OH
OH
(c) H (d) HO
HO OMe
2. Which of the following are reducing sugars?
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158 ===================== CHEMISTRY
OH OMe
(a) H
O OH
H~+~H
COOH CHpMe
(d) M e O ~ Q OH
(c)
MeO~
COOH OMe
4. Salicin (structure given below) is a glucoside, found in the base of willow tree, used in relieving pain.
dil. HC I
P+ Q
..__.,
Products
(b) Q is 2-hydroxybenzylalcohol
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Biomolecules & Polymers 159
8. The gycosidic linkage involved in linking glucose units in amylopectin part of starch is
OH OH
(a) It is pentose (b) It is pentulose (c) It is a a-anomer (d) It is a pyranose
( I ) Integer Answer
11. (a) Number of stereocentre in linear glucose = x
x+y + z= ?
12. In a mixture of equilibrium of a, ~ and open chain. %a = 36%, %~ = 63.98% and % of open chain
= 0.02%. If 20% ~ form is taken then after some time what is the% of a form?
OH
13. Glucose
@@
-----+P
10%
D.U. ofP?
14. N inhydrin reagent react with a -amino acids to give purple colour. In the reaction of Ninhydrin with
15. Amongst the following the total number of biodegradable polymer are :
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160 ===================== CHEMISTRY
(ix) Vitamin B 2
18. Number of compound which can form silver mirror on reaction with Ag+, NH 3 ?
CH OH
HO~oyNH-0-Me HO
(;J >--Z ~ (ii) HO 0~
HO
OH OH OH
OH OH
(iv) H O K
OH
OH
OH
CH 20 H
CH20H
0 I\
(v) o'V::>fHzOH (vi) 0 0
OH
pOH
'-.../
CHz- o
OH
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Biomolecules & Polymers 16 1
19. A tetrapeptide has - COOH group on alanine. This produces glycine (Gly), Valine (Val), Phenyl
alanine (Phe) and alanine (Ala), on complete hydrolysis. For this tetrapeptide, the number of possible
g-.. .:
2 1.
Match the Following
(A) Crystalline Na2 CO 3 + Sodium citrate + CuSO4 (aq. sol.) (p) Fehling Solution
(C) Alcohol
R--CH(OH}---OSONH--®'
(r)
R-CH(OH)- OSONH--(Q)/
C
0 -
NH
(Violet Red)
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162 CHEMISTRY
Passage-I
•
(I) NH20H
P2
(2) HEB / t:,.
+
(2) H /t:,.
(3) Rh/t:,.
(4) H 2SO/ t:,. Polymerisation
P3_ _ _ ___.
(S)NaOH
(6) NaOH (fuse)
+
(7) H
H+
(a) P4 + HCHO--->Novalac
H+
(b) P4 +HCHO--->Bakelite
H2NY NY NH2
(d) P4 + ~ N --+ Melami ne polymer
NH2
24. Select correct statement(s) about P5 .
(1) Zn / t:,.
P4 - - - - - - - P s
(2) 03 / H20 / Zn / t:,.
(3) NaBH4 / THF
OH
I
(c) P5 +CH3 - CH-CH2 -CHOH Polymerisation PHBV
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Biomolecules & Polymers 163
Passage-II
An a -amino acid 'A' has molecular formula C 3H 7N0 3 . ' A' on treatment with methanol in presence
ofHCl yields 'B ' [C 4 H 10N03 Cl]. 'B ' on further treatment with PC15 yield 'C' [C4 H 9N02 Cl]. Which
on acidic hydrolysis yields ' D ' [C3 H 6N02 Cl]. ' D ' on reduction with Na(Hg) in dilute acidic medium
yields alanine.
NH2 0 0
I II II
(a) H- C- C- CI (b) CH - CH -NH- C - CI
I 2 2
I
CH 0H OH
2
NH2
(c) H-
I COOH
C- (d) (a) and (b) both are possible.
I
CH CI2
RESPONSE SHEET
1. (i)@(s)@ 2. (i)@(s)@ 3. (i)@(s)@
4. (i)@(s)@ 5. (i)@(s)@ 6. (i)@(s)@
7. (i)@(s)@ 8. (i)@(s)@ 9. (i)@(s)@
10. (i)@(s)@ 11. 12.
19. 20.
ANSWER KEYS
1. d 2. a, c, d 3. a, b, c, d 4. a, b,c, d 5. a, b, c 6. a, b,c, d
7. a, d 8. a, b 9. b, c 10. b, c 11. 11 12. 36
13. 17 14. 18 15. 4 16. 3 17. 5 18. 7
19. 6 20. 3 21. A - r; B - p ; C - s; D - q; 22. A - q, r; B - p; C - s; D - t;
23. a, b 24. a, b 25. C 26. C
,1
.. . ..
\ I I I
_ \ _
Hints & Solutions :
..
I ':_
·------ _ _ _ _ _go-•
1. (d) a -form means OH on lowerside. 5. (a, b, c) All reducing sugar shows mutarotation.
Methyl-a -D-means OH is converted into - OMe. 6. (a, b , c, d)
As per structure OH on 4 th C should lie on axial (a) Fructose Tollen ' s + ve
position. (b) Sucrose is leavo rotatary.
2. (a, c, d) Except sucrose all disaccharides are (c) ~ form is more stable due to less repulsion.
reducing sugar. (d) Fact.
3. (a, b, c, d) In all the structures - OH group in 7. (a, d)
2,4 DNP
fischer proj ection lies on right hand side. G lucose - - - - +ve
4. (a, b , c, d) On hydrolysis : Tollen's
~:\JH
- - - - +ve
...___
Schiff _ _ ve
Test
..._NaHS0
_ _ 3_) - ve
(P) ~ -Gl,oo~)
8. (a, b) C 1 - C 4 a link is present to connect the
H~ linear chain C 1 - C 6 ~ link is present to connect
H OH to another chain.
9. (b, c) Glycine is optically inactive.
OH Proline is secondary aminoacid.
(2JOH 10.
So, (band c) are correct.
(b, c) Pentose sugar contains OH on carbon
atom so it is pentulose sugar. As OH group lies
on downward side so it is a -form.
11. (11) X = 4, y = 5, Z = 2
x + y+z =ll
Linear G lucose Cyclic G lucose
CHO
0
II H * OH
HO * H
* OH
H OH *
H * OH
CH20H H OH
(Aspirin) x =4 y= 5
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Biomolecules & Polymers 165
12. (36) As equilibrium maintains. 18. (7) It anomeric C contains (-OH) group then
The cone. of a, ~ and open chain remain same. it is a reducing sugar. All disaccharides are
So% a= 36%.
reducing sugar except sucrose.
CHO
H OH
H Cone. H2SO4
13. (17) HO Ala is fixed.
H OH -3H2 O
Now position for A, Band C
H OH
= 3! = 3 X 2 X 1 = 6.
OH 20. (3)
HO~
0 CH0
2
@@
21. A - r; B - p; C - s ; D - q;
~OH Fehling Solution :
0 CH
CuSO4 + Rochelle Salt+ NaOH
HO~ ~ OH
Molisch Reagent :
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166 CHEMISTRY
For 23-24: For 25-26:
NH2
I Me-OH
HO-CH 2 - CH-COOH
HCI
C3H7N03
(A)
NH2
I PCl5
HO-CH 2 -CH-C-OMe
II
0
(B)
NH2
I
Cl-CH 2 -CH-C-0-Me
II
0
(C)
0 I Zn CHO NaBH') [ OH NH2
~ I I
CHO OH Cl-CH2 - CH-COOH
(P4) (P5) (D)
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Hydrogen and
s-Block
OH
3. Which of the following statements are correct?
(a) Li < K < Na < Rb < Cs (Density)
(b) LiOH < NaOH < KOH < RbOH < CsOH (Basic strength)
(c) LiCl < NaCl < KCl < RbCl < CsCl (Melting point)
(d) K0 2 is used in purification of air
4. Which of the order are correct?
(a) Cs < Rb < K < Na < Li (Reactivity with hydrogen)
(b) LiCl < LiBr < Lil (Covalent nature)
( c) BeC12 > MgC12 > CaC12 > SrC12 > BaC12 (Ionic character)
(d) Cal2 < CaBr2 < CaC12 < CaF2 (Melting point)
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168 CHEMISTRY
5. Both Na and Li are placed in air (dry), we can get
(a) Na2 O (b) Li3 N
(d) NaOH
6. In Castner-Kellner cell, which of the following statements are true?
(a) At cathode Na combines with Hg even H 2 O has more tendency.
(b) The formation of Na-Hg amalgam provided stability and also over voltage for H 2 is high with Hg
cathode are main reason.
(c) Na-Hg+H2 O~NaOH+ Hg +H2 i
(recycled)
0
II o+ o+_... oe........_c_......o........_H
e _.. . . c . . . . _ _......H-.... e _......H···
.. o o ··o.. . . ._ _......o 11
✓ C O
II
0
(b) InKHCO 3 , HCO 3- 1 forms dimer
8
o
O=C /
0 •·•••· H -
' C=O
"-o-H······O/
e
(c) Solvay process can not be employed for the preparation of KHCO 3 because it is difficult to
separate due to more solubility.
(d) LiHCO3 exist in solid state.
8. Which of the following reaction give 0 2 as product?
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Hydrogen & s-Block Elements 169
( I ) Integer Answer
11.
12.
The total number of neutrons present in D 2 0 17
molecule (hypothetical) are?
•
The hydrogen when combined with Halogen form Hydrogen halides. IfpKa of HF, HCl, HBr and HI
arex 1,x2 ,x3 ,x4 then x 12 -x2 +x3 -x4 =?
l Polymerise
Si XHy
17. The number of moieties available for H-bonding in one molecule ofR-S0 3H.
18. Number of boiling point order which are represented correctly
(i) H 2 0 > H 2Te > H 2 Se > H 2 S
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17 0 CHEMIST RY
Column-I Column-II
•
(A) Li > Na > K > Rb > Cs (p) Melting point
(C) H2O > H 2Te > H 2Se (r) Latent heat of vaporisation
22.
Column-I Column-II
(A) /',. (p) One of the product has sp2 hybridisation central
Na2 SO4 +C+CaCO3 ~
atom
(C) KOH+NO (r) One of the product has sp3 hybridisation of central
2 4 atom
Period
Period
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Hydrogen & s-Block Elements 171
vm
(c) (d)
B.Pt. B .Pt.
Br
HCI
Period Period
(a) M.Pt.
H2Te
ttiS
Period
(b) ~H,,.p,
H 2Te
ttiS
Period
(c) ~Hvap.
Period
(d) M.Pt.
Period
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172 CHEMISTRY
Passage-II
Hydrogen peroxide is an important chemical used in pollution control treatment of domestic and
industrial effluents.
25. Which of the following incorrect regarding H 2 0 2 ?
(a) It is pale blue or almost colourless.
(b) H 20 2 is insoluble in H 20 .
(c) It can be prepared by acidifying barium peroxide and removing excess water.
(d) 2HSO-4 l (1) electrolysis H O
(2)Hydrolysis 2 2
RESPONSE SHEET
1. (i)@(s)@ 2. (i)@(s)@ 3. (i)@(s)@
4. (i)@(s)@ 5. (i)@(s)@ 6. (i)@(s)@
7. (i)@(s)@ 8. (i)@(s)@ 9. (i)@(s)@
10. (i)@(s)@ 11. 12.
19. 20.
ANSWER KEYS
1. d 2. a, b, c, d 3. a,b,d 4. a, b, d 5. a, b, c 6. a, b,c 7. a, b, c
8. b,c, d 9. b, c 10. a, d 11. 10 12. 17 13. 32 14. 6
15. 4 16. 3 17. 7 18. 4 19. 5 20. 4
21. A - p ; B - q, r; C - q ; D - s 22. A - p , r, s ; B - p , r, s ; C - p , q, r; D - p ; 23. b, c,d
24. a, b, d 25. b 26. C
... .
\ I I \ I I
_ \ ..._
Hints & Solutions :
..
I ':
•,a__ _ __
----- ·
1. ( d) Solubility order trends (c)
(1) Li2 CO3 < Na2 CO3 < K2 CO3 < ... ... . ...... H-O .........
(2) CsCl > RbCl > LiCl > NaCl > KCl
I
.....-<;)- H-.....
(3) MgF2 < CaF2 < SrF2 < BaF2 < BeF2 (exception)
.•· ~ ·•.
6H.B. 4H.B.
Hence, option (a), (b), (c) in question are incorrect.
electronegative O atom.
3. (a,b, d)
(b) LiOH < NaOH < KOH < RbOH < CsOH
basicity
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174 CHEMISTRY
Anode:
M.P.
Complete reaction.
7. (a, b , c)
Period
Option (a, b) are fact.
NaCl shows maximum M.P. because its
KHC03 is more soluble so KHC0 3 can't be
coordination number is high.
prepared.
1
(b) Na 2 0 2 + H 2 0~NaOH+H2 0 + -0 2
(ionic character) Warm 2
According to Fajan's rule, as the size of cation (c) Na 2 0 2 +Mn0 41 ~Mn+2 +02
373K
l
~
>373K
N32C03
6. (a, b, c) In Castner-Kellner cell, electrolysis of
10. (a, d) Be has relatively high tendency to form
NaCl solution (brine) with mercury cathode
complexes (high charge and small size).
and carbon anode
Cathode:
Most of the compound of Be are highly soluble
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Hydrogen & s-Block Elements 175
11.
19.
12. (17) HF HCl HBr HI
Z=2, A=3 ; 2+3 = 5.
3 -7 -9 -10
20. (4) Be+z show coordination no. 4.
9+7-9 + 10=17.
2 1. A- p ; B - q , r; C - q; D - s;
13. (32) Si 10H22 is the maximum chain length that
Li > Na > K > Rb > Cs Melting point order
silicon can achieve so x + y = 32.
due to stronger
14. (6)
metallic bond.
HN N
2 -... ~ '\. .,,,NH2 Boiling point due to
' C C' ··
Pyrolysis I II mass and latent heat
.N N.
-~C / " of vapourisation due
I to B.P.
!'!H2
HzO > HzTe > Hz Se Boiling p oint due to
nuclear spin.
22. A - p , r, s; B - p , r, s; C - p , q, r; D - p;
Lithium halide generally form trihydrate. NazSO4 +C+CaCO3 ➔ Na2 CO 3 +CaSO4 j,,
(sp 2 ) (sp3)
17. (7)
\\ ,/~
NaCl + NH4 HCO3 ➔ NaHCO3 j,, + NH4 Cl
·o· (sp2) (sp3)
II
R- S- 0 - H ----------· Total 7 H.B.
II 2KOH+4NO ➔ KNO2 + NzO+H2O
sp2 neutral sp3
oxide
18. (4) In Group hydrides, the molecule which NazCO3 + Ca(OH)z ➔ CaCO3 + NaOH
sp 2
can show hydrogen bonding possess highest
more than boiling point is more. As H 2O can show hydrogen bonding so correct
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176 CHEMISTRY
B.Pt.
68X20
So, for 20 lt = - - - = 60 gH2 0 2
22.7
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p-Block
Elements
(d) Ag and C
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178 CHEMISTRY
(b) H 20 2 and 0 2F 2 have similar structures, hence the 0- 0 bond of the two molecules are identical
(a) N 20
(c) C 6H 6
(a) When BF3 is treated with excess ofNaF in acidic aqueous solution gives NaBF4
(b) When BC13 is treated with excess of NaCl in acidic aqueous solution gives H 3B03
(c) When BBr3 is treated with NH(CH3)i in a hydro-carbon solvent gives B[N(CH3)ih
8. Which one of the following arrangements does not give the correct picture of the trends indicated
against it?
(a) K 20
(c) OF2
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p-Block Elements 179
( I ) Integer Answer
11.
12.
The numbers of P - 0 present in (HPO3h. •
3.55 g of a bleaching powder when treated with acetic acid and excess of KL Liberated iodine required
30 ml of 0.5 N sodium thiosulphate solution. The percentage of available chlorine in the sample is?
13. Number of Dichloroderivatives of benzene are x and for inorganic benzene are y then x + y = ?
15. Number of oxygen atom shared with other unit in cyclic silicate having general formula (SiO 3- 2 )n.
Li Li
(i) NH 4 NO3 ~ (ii) N H 4 NO 2 ~
Li Li
(iii) NH 4 IO 3 ~ (iv) N H 4 ClO4 ~
Li Li
(v) (NH4 )zCr2 O 7 ~ (vi) (NH4 )3PO4 ~
(vii) NH 4 Cl ~ (viii) NH 4 B r ~
Li
(ix) (NH 4 )z CO3 ~ (x) (NH 4 )zSO4 ~
Zn Pb
s
ZnO XeF 6
BeO BN AlN
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180 ===================== CHEMIST RY
g-..:
2 1.
Match the Following
Match the following.
Column-I Column-II
•
(A) H S 0 H 20 (p) dibasic
2 2 8
Column-I Column-II
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p- Block Elements 181
Passage-I
Following flow sheet is used to prepare pure Silicon. Answer the questions based on it.
•
co
__
C._l'i_> [ } [ ] t
1Cl2
A
Pure SiCl4
Impurities
Passage-II
D + E d
(black)
1 T > 800°C
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182 ===================== CHEMISTRY
RESPONSE SHEET
1. (i)@(s)@ 2. (i)@(s)@ 3. (i)@(s)@
4. (i)@(s)@ 5. (i)@(s)@ 6. (i)@(s)@
7. (i)@(s)@ 8. (i)@(s)@ 9. (i)@(s)@
10. (i)@(s)@ 11. 12.
19. 20.
ANSWER KEYS
1. a 2. d 3. b 4. a, b 5. a, d 6. a, b , d 7. a, b, c, d
8. a, d 9. a, b, c 10. c, d 11. 12 12. 15 13. 7 14. 6
15. 2 16. 6 17. 5 18. 5 19. 5 20. 5
21. A - p, q, r , s, t, B - p , q, r , s, t, C - r , s, t, D - q, r , s 22. A - p; B - r; C - q; D - s
23. a 24. C 25. b 26. C
1.
EB F
EB _,,,, F _,,,, o = o
Fe
0 = O' ~ F'
Both PF61 & SbF61 have octahedral structure. Though 0 2 F 2 and H 2 0 2 have similar structures
6. (a, b , d)
Azide N = N= N
3.
e £ EB e
sp
(a)N = N~ O
sp
(b)H-C:: C - H
sp
(c) © s/
(more no. of e- are shared (d)O = C= 0
2
sp
then bond is stronger bond
7. (a, b , c, d)
and shorter bond)
The F- ion is chemically hard (non-polarizable)
(more repulsion between
and fairly strong base. BF3 is a hard and strong
electrons)
lewis acid with high affinity for the F- 1 ion.
5. (a, d) In 0 2 F 2 the O - 0 bond is shorter than
Therefore F- 1 combines w ith BF 3 forming
that in H 2 0 2 due to resonance.
BF4_1_
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184 CHEMISTRY
Excess P-1 and acid prevent the hydrolysis = 30 ml of0.5 N Cl2 solution
of BF3, BC13 hydrolysis vigorously in water % available Cl2
Cl Cl
Cl
Cl2 > Br2 > F 2 > 12 I
H......._ B ,....... c1
and electron gain enthalpy of Cl > F due to N'..,.. ' N
IO I
B . B
more size and less electron-electron repulsion. H/ ' N'..- "'-H
9. (a, b , c)
I
H
H Cl
H-Be-H I
sp H......._
N
/t...._N,.......c1 H......._ /B...._ /H
N N
IO I I O I y= 4
,.......B...._N/B......._ B B
H / 'N/ "'-H
H I H
I
Cl Cl
3+ 4= 7
sp
= 30 ml of0.5 12 solution
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p-Block Elements 185
0 0 0 0
II II II II undergo dimensation.
/p'\ '\,P<\ ,P'\ /p'\ 19. (5) P 4 , S, Cl2 , XeF 6 , Br2 can undergo
HO I o~IOHoXIOHo OH
OH
I OH disproportion.
/ 20. (5)
17. (5) 2 1. A- p , q, r , s, t; B - p , q , r , s, t; C - r , s, t; D - q, r , s;
(a) p , q, r , s, t
Room
temp.
reducing agent.
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186 CHEMISTRY
(b) p , q, r, s,t (r) HNO2 can act as both oxidising and
reducing agent.
temp
(s) NO~, No3- 1 can act as monodentate
ligand.
(q) so/- can act as flexidentate ligand.
22. A - p; B - r ; C - q; D - s;
(r) SO 3 2- can act as both oxidising and
(a) P4 + N aOH + N H 3 ~ PH3 + H 2 O + IH3PO2 I
reducing agent.
(d) q, r, s
SiC14 + 2Mg----4 Si + 2MgC12
Room
temp. SiC14 is liquid can be purified by fractional
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d&f-Block and
Metallurgy
3. What will be the correct representation of quantum numbers for the last electron entered into Ce?
n l m s n l m s
(a) Zn (b) Fe
(c) Pt (d) Cd
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188 ===================== CHEMISTRY
(a) Pb (b) Fe
(c) Zn (d) Al
(a) distillation
8. Which of the following statements is/are correct about the making of blue prints?
(a) Ferric oxalate or citrate is reduced to ferrous salt on being exposed to light.
(d) White lines are obtained in place of the ink drawing on a deep blue background.
9. Which of the following reaction takes place in the reduction zone of blast furnace?
(a) CO 2 +C~2CO
(d) FeO+CO~Fe+CO2
(b) Zone refining can be done for Si, B, Ga, In, Ge.
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d & f- Block and Metallurgy 189
( I ) Integer Answer
12. If x 1, x 2 and x 3 are the oxidation state of Fe in haematite, magnetite and Iron pyrites than
13. How many of the following oxides of transition metal are basic in nature?
17. Among the following elements, number of elements for which zone refining can be used is
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190 ===================== CHEMISTRY
Column-I Column-II
•
(A) Metal extraction from galena (p) Leaching with complexing agent or alkali
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d & f- Block and Metallurgy 19 1
(J) Ni2 +
(K) Cu 2 +
(L) c u+
(M) Zn2+
Passage-I
•
In the froth flotation process, finely divided ore, water, pine oil and sodium ethyl xanthate are taken
together and air is blown from the bottom at the container. Froth are formed, these froth are collected
(d) Mercaptobenzthiazole
24. Which of the statements are correct regarding froth flotation method?
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192 CHEMISTRY
Passage-II
IfKOH
B
Mn02 KOH
A I Cold water
little alkali
Green
Solution
On
evaporation
is used
IfNaOH
C
Pyrolusite Green melt is used
25. Compound A is
RESPONSE SHEET
1. (i)@(s)@ 2. (i)@(s)@ 3. (i)@(s)@
4. (i)@(s)@ 5. (i)@(s)@ 6. (i)@(s)@
7. (i)@(s)@ 8. (i)@(s)@ 9. (i)@(s)@
10. (i)@(s)@ 11. 12.
19. 20.
ANSWER KEYS
1. C 2. a, b,c 3. a, b, d 4. b,c 5. b,c 6. a, b,c 7. a, b
8. a, b, d 9. b,c, d 10. a, b 11. 24 12. 69 13. 5 14. 4
15. 5 16. 4 17. 3 18. 2 19. 3 20. 4
21. A - r, s; B - p , q ; C - r; D - p , q 22. A - s; B - s; C - p; D - v; E - v; F - u; G - r; H - p
23. a, b, c, d 24. a, b, d 25. b 26. a
,, .
Hints & Solutions : l ':
- - - - -17'
1. (c) CuSO4 · 5H2 O ⇒ Blue vitriol 7. (a, b) Zinc having low boiling point distill
over on boiling leaving behind Ag. If boiled
FeSO4 · 7H 2 O ⇒ Green vitriol
with NaOH, zinc dissolves due to formation of
ZnSO4 · 7H 2 O ⇒ White vitriol
Na2ZnO2 but silver is unaffected.
Fe+2 +KMnO4 -H_+___,.Fe3+ +Mn2 + 8. (a, b , d) The oxalate or citrate ion reduces
2. (a, b , c) Melting point oder: ferric salt to ferrous salt in the presence of light
W > Mo > Cr (photochemical reduction) which gives blue
Cr > Fe > Mn colour w ith potassium ferricyanide (Tum bull's
Cu > Au > Ag blue) so white lines are obtained in place of the
In a series with increase in number of unpaired ink drawing on a deep blue background.
electrons strength of metallic bond increases, 9. (b, c, d) Blast furnace reduction zone are given as
thus melting point increases but Mn having Fe2 O 3 +CO~Fe3 O 4 +CO2
stable d 5 configuration have low melting Fe3O 4 +CO~FeO+CO2
point than Cr and Fe. Second and third series
FeO+CO~Fe+CO2
element have m ore melting point because of
metal-metal bonding. 10. (a, b) Van arkel method is used for Zr, Ti.
3. (a, b, d) Last electrons enters into 4f sub-shells. Zone refining can be done for Si, B , Ga, In, Ge.
Electrolysis
15. (5) Copper glance Cu2S
Al2O 3 +Na 3AlF6 +CaF2
Copper pyrite CuFeS 2
I 2 I
Atacamite Cu2Cl(OH) 3
22. A - s; B - s; C - p; D - v; E - v; F - u; G - r; H - p;
Malachite Cu(OII)i.CuCO3
I - w; J - p; K - t; L - s; M - s;
Azurite Cu(OH)i.2CuCO3 The species which contains unpaired electrons
16. (4) Magnelium Al (98%) in ground or excitate states are colourfull Zn2+,
Duralumin Al (95%) Sc 3+, Ti4 +, cu+ contains O unpaired electrons,
Alnico Al (20%) so they are colourless.
N ickeloy Al (95%) 23. (a, b , c, d) All can be used as collector.
17. (3) Zone refining: 24. (a, b , d) ZnS+NaCN~[Zn(CN)4 ] 2- J.
Si, B, Ga can show zone refining. due to surface tension, bubble formation takes
Total= 3. place.
18. (2) CuFeS 2 cu2+
For 25-26:
19. (3) Camallite
KOH 2- Cold water Green
KCl · MgC12 · 6H2O MnO2-----+ MnO4 - - - - - .
(A) little alkali Solution
3 chlorine atom.
20. (4) Oxide ores= 4 K2Mn04::jOH
(8)
cilia Cuprite .-N- 3i
_ M_n_0_ __-1-
0H- 0-, Na0H
4 2
PbS Galena (C)
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196 ===================== CHEMISTRY
5. In w hich o f the following inclu ding metal atleast 5 a tom s are in a line?
,i
(b) NH4NO3 ~NO2 + NH3
(c) NO2 + starch iodide pap er ➔ Blue colour
(slowly)
(d) Bc 1, 1-1 and No2- 1 interfere the brown ring test for N o 3- 1 .
8. W hic h of the following ions can be separated by using NH4C l and NH4OH ?
Na0H
(b) Cr 3+ Na0H
Cr(OH)3
excess
[Cr(OH) 4 r 1 Hz0z
OH
cr02-
4
AgN03
Ag 2CrO4
green (Brick red)
(c) Co(N03)z
Al2O3 l -2drop Al2O3.CoO
(Pink mass)
Bi+3 H2S
(d) Bi 2S3 .J,, (Black) .
( I ) Integer Answer
11. Total number of compound wh ose hybridisation is d 2 sp3 :
[Cr(H 2O) 6] 3+, [Cr(CN ) 6] 3- , [Cr(H 2O) 6]2+, [Mn(Br) 4]2-, [Mn (NH 3) 6]2+, [Fe(NH 3) 6] 2+,
•
[Co(H 2O)6]3+, [Co(C2O4h] 3- , [IrC16] 3- , [NiF612- , [AuC14r 1
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Coordination Compounds & Qualitative Analysis 197
0 0
[Fe(1t -C5H 5 h] , [1t(cr - C 5 H 5 h (1t-C5H 5 h] , [Fei(CO)9 ], [Coi(CO) 8 ], [Mn(CO)6 ], [Mn(CO)5 ],
If x 1 + x 2 + x 3 are possible co-ordination isomer of given complex compound respectively then value
ofx/+x/ + x/ = ??
N H2
16. Total number of stereoisomer possible for [M(AB )a2 bc] type complex?
19. A small amount of mixture is treated with dil. H 2 SO4 solution, how many of the following anions can
give positive test?
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198 CHEMISTRY
Column-I Column-II
•
(A) dsp2 (p) [NiF6]2-
(u) [Fe(CO)5]
(v) [Fe(EDTA)r
22. Which of the anions in the column-I shows one or more observation from the column-II
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Coordination Compounds & Qualitative Analysis 199
Passage-II
If ligand also contains chiral centre then number of stereo-isomer increases and is calculated as like
we calculate in organic chemistry.
25. [Pt(bn)2 ] 2+ posseses
(a) 5 Geometrical isomers (b) 4 Geometrical isomers
(c) 6 Total isomers (d) 7 Total isomers
RESPONSE SHEET
1. Ci)@@@ 2. Ci)@@@ 3. Ci)@@@
4. Ci)@@@ 5. Ci)@@@ 6. Ci)@@@
7. Ci)@@@ 8. Ci)@@@ 9. Ci)@@@
10. Ci)@@@ 11. 12.
19. 20.
21. IAI 1
8 1 lcl lnl 22. IAI 1
8 1 lcl lnl
23. Ci)@@@ 24. Ci)@@@ 25. Ci)@@@
26. Ci)@@@
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200 CHEMISTRY
ANSWER KEYS
1. c, d 2. a, b, c, d 3. a, b, d 4. a, b, c 5. b, d 6. a,c, d 7. a,c, d
8. b, d 9. a, b, c, d 10. a, b, d 11. 6 12. 6 13. 4 14. 38
15. 9 16. 12 17. 16 18. 52 19. 3 20. 5
21. A - t; B - q, s ; C - r; D - p , v ; E - u 22. A - q; B - p , q, r, s; C - p , q; D - p
23. b 24. b 25. a, d 26. b, c
,, ,
.. ' '. C
\ I I
_ \ ._
Hints & Solutions ..
: I :
l---- - - - -IY'
1. (c, d) 3. (a,b, d)
(a) :NHi - :NHi will form three membered ring (a) Fe 0 = 4s 2 3d6
towards metal so can not act as chelating ligand.
I I
both N atom act as donor atom (b) due to ~ 0 > P (always)
(c) 5 and 6 membered rings are stable. (c) As EDTA3-is pentadentate ligand
- OOC - CH 2 CH 2 - COO-
(d) [Fe(H2 O)5NO]SO4
+ 5 (0) + 1 - 2 = 0
' CH - ..
2 CH2- N. /
X
-ooc - CH/ ' CH2 - COOH
x -l=0 ;x = +l
(d) In Zeise's salt, C = C receives back donation
2. (a, b , c, d)
in n* orbital, B.O . .J.. hence B.L. increases so it
(a) [Ni(CN) 5]3-: dsp3 : sq. pyramidal
will greater than 1.33 A (C = C).
(b)Ncs- 1 is WFL
4. (a, b , c)
OXI
(c)
)= N N=C N/
'-Pt/
" N *
({f 101 (J<]
I
& [
oc co co co
"'-.I
(d) OC - -Mn - - Mn - - CO
I/
oc
/ Ico I"'-.
co co
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Coordination Compounds & Qualitative Analysis 20 1
7. (a, c, d) [Mn(CO)6 ] = 25 + 0 + 12 = 37
Li
(a) NaNO3 ~ NaNO2 +02 [Mn(CO) 5] = 25 + 0 + 10 = 35
(c) NO2 + starch iodide paper ➔ Blue colour [Fe(C2 O4) 3]3- = 26 - (3) + 3 x 4 = 35
(slowly) [Pb2+(EDTA) 2- = 82 - 2 + 1 x 12 = 92
(d)Bc, 1- and NO2- intefere in NO3 brown [Zn(gly)2] 0 = 30 - 2 + 2 x 4 = 36
ring test
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20 2 CHEMISTRY
2+ 2+
Cu Cu
- -
CC NO2 Cl NO2-
4 0 0 4
1l
3
Not +-2- --....::....--+--=-------'
2 2 ~
::..
7 same
possible 1 3 3 1
Methylene blue
0 4 4 0 D .U. = 9
Cr
3+
Cr
3+ A '-.__ I/ a
( / M'-.__
N H3 SCN
-
NH3 SCN B I a
6 0 0 6 C (2)
5 5
4 2 2 4
+.;~-.....::----1---=---....:!.--+-l-+Same
3 3 3 3
2 4 4 2
I 5 5 I
0 6 6 0
2+
ca3+ Pt
1 7. ( 16) A ll are black coloured ppt.
NH3 N03 SCN NH3 NH3 SCN
5 I 0 0 0 4 18. (52)
5 0 0 I 3 T :s; 40°C
4 0 3 (NH4)z M00 4
(NH 4)3PO4 .12MoO4
+ HN03
3 2 2 0 2 Caneiry yellow ppt.
2 3 3 0 1 Not
possible 52 o-atoms are present in product.
4 4 0 0
19. (3) The group A radicals give +ve test w ith
5 co-ordination isomers
2 2 2
dil. H 2 SO 4 w hile group B radicals w ith cone.
XJ + Xz + X3 = 2 2 + 32 + 52
H2 SO4 .
= 4 + 9 + 25 = 13 + 25 = 38
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Coordination Compounds & Qualitative Analysis 203
21. A - t; B - q, s; C - r ; D - p , v; E - u
[NiF6 ] 2- : N i4+ : more charge so .10 > P even F
is W FL so it will have hybridisation d2sp 3 So32- + KMn O 4 ----4 Mn2+ +SO2-
4 +H 2O
colourless
[Ni(CO)4] : Ni= 4s 23d8
t
CuC03 ~ CuO + CO2
1t It It 11~ It I ~ 11 xx Ixx IxxI I
I bluish (B) (C)
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C:\0--------------------�===· :
CHEMISTRY
For 25-26 Hence,' geom,mca I =
an d�7 total isomers are
�e Me
N
)r<-f
N
Me )= �Me
0.1.
Me Me 0.1.
N
"
N
"'-rt/ J
/
N N ·,,,,,_
Me)= ⇒ (2)
"Me
0.A.=2
6 total isomers
25. (a, d)
26. (b, c)
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