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SRI CHAITANYA IIT ACADEMY - VSP

SEC :
SUB : CHEMISTRY
Passage I
Hoffmann bromamide reaction involves conversion of a carboxylic acid amide into an amine with a loss
of a carbon atom on treatment with aqueous sodium hypobromite. Thus Hoffmann results in shortening
of a carbon chain
Mechanism of the reaction is :

!".
#$%
&
Ph NH
#B%
& &
Ph CH NH
#'%
(
Ph NH CH
#)%
!&. *hich of the following will not give Hoffmann bromamide reaction.
#$% #B% #'% #)%
!(.
NH
O
O
KOBr
#$%+ Product#$% is
#$%
NH
2
O K
+
O
#B%
NH-CH
3
O
OH
#'%
&
NH
&
NH
#)% ,one
Passage II
*hen a crystalline compound - is heated with
& & .
K Cr O
and concentrated
& /
H SO + a reddish brown gas $
is evolved. 0n passing $ into caustic soda+ a yellow solution of 1 is formed. $ yellow precipitate of ' is
Sri Chaitanya Page 1 Vizag

obtained when a solution of 1 is neutralised with acetic acid and then treated with a lead acetate solution.
*hen - is heated with ,a0H+ a colourless gas is evolved which+ when passed into a solution of
[ ]
& /
K HgI
+ gives a reddish brown precipitate of )
!/. 'ompound #-% is :
#$%
/
NH Br #B%
/
NH Cl #'%
/ &
NH NO #)%
/ (
NH NO
!2. If the solution 1 is colourless+ which of the following ions would not be present in the solid -3
#$% Cl

#B%
Br

#'%
(
NO

#)%
&
NO

!4. *hich of the following is the composition of the brown precipitate3


#$%
&
HgI
#B% ( )
&
Hg NH I
#'%
HgO
#)% ( )
&
. HgO Hg NH I
Passage III
The apparatus consists of three temperature 5ac6eted ".!!! 7 bulbs connected by stopcoc6s. 1ulb $
contains a mixture of H
&
0#g%+ '0
&
#g%+ and ,
&
#g% at &2
o
' and a total pressure of 24/ mm Hg. 1ulb 1 is
empty and is held at a temperature of .!
o
'. 1ulb ' is also empty and is held at a temperature of "8!
o
'.
The stopcoc6s are closed+ and the volume of the lines connecting the bulbs is 9ero. '0
&
sublimes at .:
o
'+
and ,
&
boils at "84
o
'
!.. The stopcoc6 between $ and 1 is opened+ and the system is allowed to come to equilibrium. The pressure
in $ and 1 is now &"8 mm Hg. *hat does bulb $ contain3
#$% '0
&
#B% '0
&
; ,
&
#'% ,
&
#)% '0
&
+ ,
&
; *ater
!:. 1oth stopcoc6s are opened+ and the system is again allowed to come to equilibrium. The pressure
throughout the system is ((.2 mm Hg. *hat does bulb 1 contain3
#$% '0
&
#B% '0
&
; ,
&
#'% ,
&
#)% '0
&
+ ,
&
; *ater
!8. How many moles of '0
&
are in the system3
#$% !.!& #B% !.!/ #'% !.!4 #)% !.!:
Passage I<
Sri Chaitanya Page 2 Vizag

"!. The compounds #P% and #=% are respectively
#$%
& & & (
+ Na O Na CO
#B%
& & &
+ Na O Na S
#'%
& & (
+ Na O Na SO
#)%
& &
+ Na O NaOH
"". The compound #T% is
#$%
& (
Na CO
#B% NaOH #'% ( )
&
Ca OH
#)%
/
CaSO
Passage <
'onsider the interconversion of nitrosotriacetoaminie into nitrogen+ phorone and water.
C
N
O
ONO
CH
3
CH
3
C H
3
C H
3
( ) aq
( ) ( )
& &
, g H 0 + l
C
C
C
O
CH
3
C H
3
CH
3
(
'H
+
&! 6> ? mol
( ) Phorone
( ) aq
The reaction is "
st
order in each direction+ with an equilibrium constant of "!
/
. The activation energy for
the bac6ward reaction is 2../2 6>?mol. $ssume its $rrhenius preexponential factor as "!
"&
s
"
"&. *hat is the expected forward constant at (!! @+ if we initiate this reaction starting with only reactant3
#$% "!
&
#B% "!
4
#'% "!
:
#)% "!
/
"(. If the change in entropy of the reaction is !.!. 6> @
"
mol
"
at " atm pressure. 'alculate upto which
temperature the forward reaction would not be spontaneous3
#$% T A &:2.. @ #B% T B &2! @ #'% T A (/!.& @ #)% T B &!! @
"/. 'alculate @
p
of the reaction at (!! @
#$%
/ "
&./ "! atm

#B%
/
"! atm #'%
/
&/.4 "! atm #)%
& "
&.:& "! atm

Passage <I
'ompound #'%
F
3
C C
O
C(CH
3
)
3
was prepared in a three step sequence from ethyl trifluoroacetate.
The first step in a sequence involved treating ethyl trifluoroacetate with ,H
(
to give a compound #$%+
which on heating with #-% gives #1%. #1% on treatment with an orangometallic #C%+ followed by hydrolysis
produces #'% . 1ased on above passage attempt the following questions:
"2. Dtructure of #$%+ would be
#$%
N H
2
OCH
2
CH
3
O
#B%
N H
2
CF
3
O
#'%
F
3
C OCH
2
CH
3
O
#)%
O
F
3
C
OCH
2
CH
3
"4. Dtructure of #1% + would be
#$%
F
3
C C
O
NH
2
#B%
F
3
C CN
#'%
F
3
C CH
2
CN
#)%
F
3
C CH
2
NH
2
".. #-% + should be
#$% 1a0
&
#B% H
&
0
&
#'% P
/
0
"!
#)% ,
&
0
P$DD$EF <II
)iamond is a crystalline allotrope of carbon+ which crystalli9es in a (dimensional lattice. Fach
carbon forms four bonds with other carbon atoms. The unit cell of the diamond lattice can be
thought of containing carbon atoms present at all ''P positions as well in alternate tetrahedral
voids. $ssuming contact between nearest atoms+ answer the following
":. ,umber of carbon atoms per unit cell of diamond structure is
#$% / #B% : #'% "& #)% data insufficient
"8. *hat is the fraction of length covered along the body diagonal of the cubic unit cell by carbon atoms3
#$% !.2! #B% !.(/ #'% !..2 #)% !.&2
Sri Chaitanya Page 3 Vizag

&!. How much fraction of area of one face is covered by atoms3
#$%
(
(&

#B%
4
(&

#'%
8
(&

#)%
(
4/

P$DD$EF <III
$n orange colored compound #-% on heating decomposes to form a solid and gases mixture which
contains a gas #C% and
&
H O
vapour. #C% on treatment with
&
CaC
gives #G%. #G% on hydrolysis with
hot water liberates a gas #P% which when added to
& &
Hg Cl
results in the formation of blac6
precipitate
&". The compound H-I is
#$% ( )
/ (
&
NH CO
#B%
& & .
K Cr O
#'% ( )
. / &
&
NH Cr O
#)%
& & .
Na Cr O
&&. The compound #C% is
#$%
&
NO
#B%
&
N O
#'%
(
NH
#)%
&
N
&(. *hat would be the colour if solution of #P% is added in excess to
&
Ni
+
solution
#$% red #B% green #'% colour less #)% blue
P$DD$EFI-
CH
3
( )
"%MeMgI H
H 0
&
$l'l Gn Hg H'l HJ De
(
H
& &%H 0 &
(
&
'H '0 0 $ 1 ' ) F J
+


+
+
&/.
09onalysis 0H +
K FK

ma5or product
#$%
CHO
CH
3
Me
#B%
Me
O

#'%
Me
OH
#)%
Me
CO
CH
3
&2. ,o. of possible structural isomers for J is
#$% & #B% "! #'% "/ #)% 4
&4.
mononit ration
J produces
#Ma5or product%
#$%
C H
3
CH
3
NO
2
#B%
C H
3
CH
3
NO
2
Sri Chaitanya Page 4 Vizag

#'%
C H
3
CH
3
NO
2
#)%
NO
2
CH
3
CH
3
P$DD$EF L-
Pinacol is a "+&+ diol which on treating with acid produces pinacalone#6etone%. It is an
intramolecular rearrangement. The reaction starts with the protonation of hydroxyl group
followed by elimination of water and formation of carbocation. The carbocation is then stabili9ed
by *hitmore"+& shift
R C
R
C
OH
R
R
OH
R C
OH
2
R
C
OH
R
R
+
H
+
R C
R
R
C
+
OH
R
R C
+
R
C
OH
R
R
=

Dhift of #"+&%
R C
R
R
C
O
R
H
+

&..
OH OH
NO
2
CH
3
H
+
( ) Pr oduct '
The product K'K is
#$%
O
C H
3
NO
2
#B%
O
NO
2
CH
3
#'%
O
O
2
N
CH
3
#)%
O
CH
3
NO
2
&:. *hich of the following a compounds+ on pinacolpinacalone rearrangement produces a compound
which gives a precrpitate with @0I 3
#$%
CH
3
OH
OH
CH
3
#B%
C
2
H
5
OH
C
2
H
5
OH
#'%
CH
3
OH
CH
3
OH
#)%
Ph
OH
CH
3
OH
&8.
Sri Chaitanya Page 5 Vizag

Mg?THJ H
H 0
(
- C
+
+
C Ph
CH
3
Ph
C
O
CH
3
*hich of the following is not correct about the compound - and C 3
#$% #-% is can be reduced to "phenylethane on treating with
2 & / &
, H ? ' H 0

#B% #-% on treating with


&
H , 0H? H
+

followed by treating with P'l


2
produces two amides
#'% #C% may be obtained by the crossed reductive coupling between acetone and ben9ophenone
#)% #-% gives yellow precipitate with ,a0I
P$DD$EF L-I

!
2!! ' <
&
'0
M +
( ) = ( ) P
&
'0
( ) T
2!N ,a0H
M
Flectrolysis
&
D0
( ) D
&
H at anode
( ) <
( ) u
'0
(!. < and P can be
#$%
(
'a0+ 'a'0
#B%
& & (
,a 0+ ,a '0
#'%
& (
,a'l+ ,a '0
#)%
& (
,a0H+ ,a '0
(". M and D can be
#$%
& & (
,a'l+ ,a D 0
#B%
& & /
,aH+ ,a D 0
#'%
. & &
,aH+ ,a D 0
#)%
& & /
,a0H+ ,a D 0
(&. =+ u+ T can be
#$%
H'00,a+ ,a0H+ H'H0
#B%
&
H'00'u+ 'u'l H'00Ft +
#'%
( &
'H '00,a+ 'u'l + H'H0
#)% ,one
P$DD$EF L -II
To find the reaction order with respect to each reactant+ one should loo6 at the exponents in the rate law+
not the coefficients in the balanced chemical equation. $nd one method of determining the values of the
exponents in a rate law is to carry out a series of experiments in which the initial rate of reaction is
measured as function of different sets of initial concentrations. 'onsider for example the oxidation of
iodide ion by hydrogen peroxide in an acidic solution
( ) ( ) ( ) ( ) ( )
O
& & ( &
H 0 aq O(I aq O&H aq I aq O&H 0 l
-

The rate of formation of the redcoloured trioxide ion


(
I ?Pt
-

D


can be determined by measuring the rate
of appearance of the colour. Jollowing are initial rate data at&2
!
'.
Fxperiment Initial [ ]
& &
H 0
Initial
I
-



Initial rate of
formation of ( )
(
M?D I
-
" !."!! !."!!
/
"."2 "!
-

& !."!! !.&!!
/
&.(! "!
-

( !.&!! !."!!
/
&.(! "!
-

/ !.&!! !.&!!
/
/.4! "!
-

((. The rate law for the formation of


(
I

is
#$% =ate Q [ ]
& &
6 H 0 I
-



#B% =ate Q [ ]
( &
O
& &
6 H 0 I H
-



#'% =ate Q [ ]
&
O
& &
6 H 0 H



#)% =ate Q [ ]
(
& &
6 H 0 I
-



Sri Chaitanya Page 6 Vizag

(/. The value of the rate constant is
#$%
/
"."2R"! #B%
/
&.(!R"! #'%
&
"."2R"!
-
#)%
&
&.(!R"!
-

(2. *hat is the rate of formation of
(
I
-
when the concentrations are[ ]
& &
H 0 Q !.(!!M
+ and
I Q !./!! M
-



3
#$%
&
"."2R"! M?s
-
#B%
(
"."2R"! M?s
-
#'%
(
".(:R"! M?s
-
#)%
/
&.(!R"! M?s
-
P$DD$EF -III
( )
& /
& /
&
(
&
S
( / ( ( & &
/
&
&
+
# %


+ +

H O HgSO
H
H SO
CO
Cl h
KMnO
pyrene HC CH CH MgBr A B gas
C H O C H O C
CH COOH

(4. The molecule


( / (
' H 0
in sequential reaction is
#$% H0 'H Q 'H '00H - - #B%
&
T
'H Q ' '00H
OH
-
#'%
(
TT TT
'H 0H
O O
C C - - -
#)%
&
TT TT
H 'H 0H
O O
C C - - - -
(..
/
@Mn0
( & &
Hot al6aline
' H 0 Products. 0ne of the products is
#$%
T
'H0
'H0
#B%
T
'00H
'00H

#'%
&
0 Q 'H 'H '00H - -
#)%
(
TT
'H '00H
O
C - -
(:. In the sequential reaction+ if instead of ( )
& (
(
'0 + 'H ' 1r -
is used. Product will be
#$% H' H' #B% ( )
(
(
'H 'H
#'% ( )
(
(
H' '' 'H
#)% ( )
(
(
1r'H Q 'H ' 'H -
P$DD$EF L-I<
*hen two forms of allotropes exist in dynamic equlibirium at a particular temperature+ it is called
enantiotropy. Monotropy is an allotropy in which one allotrope is stable under normal conditions+ the other
allotrope being less stable for ex: 0
&
is more stable than 0
(
. The allotropy of sulphur is much more
complicated than for other elements except for carbon : e.g. liquid sulphur exists in two forms. The pale
yellow mobile form and dar6 viscous form are in equilibrium with each other. The rapid and reversible
gelation of liquid sulphur was observed in the temperature range
!
"4! "82 C . <ariety of crystalline and
amorphous forms of sulphur result by adopting suitable processes
(8. *hich of the following is cause of allotropy3
i% It is due to difference in crystalline structure
ii% )ifferent atomicity
iii% It may be due to difference in nuclear spin
#$%
+ i ii only
#B%
+ ii iii only
#'%
+ i iii only
#)%
+ + i ii iii
/!. *hen sulphur is heated at/2( @+ if forms
#$% Cellow mobile liquid #B% $mber coloured viscous liquid
#'% 'olourless mobile liquid #)% =eddish vapours
/". *hen molten sulphur is poured in cold water+ the allotrope of sulphur formed is
#$% =hombic #B% Monoclinic #'% Plastic #)% colloidal
P$DD$EF -<
#F% +a compound U#G% L 4 Heneicosen""one V has been synthesi9ed using following reaction sequence
Sri Chaitanya Page 7 Vizag

The molecular formula of #'% is
&" /!
C H O
and is same for compound #F% too
/&. The structure of compound #1% is
#$%
( )
2 "" & & &
n C H C C CH CH CH Br
#B%
( )
2 "" & & &
n C H C C CH CH CH Cl
#'%
C C
H H
(n-C
5
H
11
) CH
2
CH
2
CH
2
Br
#)%
C C
H H
(n-C
5
H
11
) CH
2
CH
2
CH
2
Cl
/(. The product #'% in the reaction sequence will be
#$% ( ) ( )
2 "" & & & "! &"
n C H C C CH CH CH n C H
#B% ( ) ( )
2 "" & & "! &"
n C H C C CH CH CHOH n C H
#'% ( ) ( ) ( )
2 "" & & & "! &"
n C H C C CH CH CH CH OH n C H
#)%
C C
H H
(n-C
5
H
11
) CH
2
CH
2
CH
2
CH(OH)(n - C
10
H
21
)
//. The correct structure of compound #F% will be
#$%
C C
H H
(n-C
5
H
11
) CH
2
CH
2
- CO - CH
2
(n - C
10
H
21
)
#B%
C C
H H
(n-C
5
H
11
) CH
2
CH
2
CH(OH)CH
2
(n - C
10
H
21
)
#'%
C C
H H
(n-C
5
H
11
) CH
2
CH
2
CO
2
H
#)%
C C
H H
(n-C
5
H
11
) CH
2
CH
2
CH
2
C(n - C
10
H
21
)
O
P$DD$EF -<I
Jor a solution of a salt at a specified concentration the product of the concentration of the ions+ each
raised to the proper power is called the ionic product ( )
ip
K
. Thus+ for a saturated solution in equilibrium
with excess solid+ the ionic product is equal to its solubility product ( )
sp
K
. If the ionic product of the
solution is less than the corresponding solubility product+ it means that the solution is unsaturated
Sri Chaitanya Page 8 Vizag

/2. The concentration of Ag
+
ions in a given saturated solution of
! 2
&2 ".&2 "! AgCl at C is g

ion per litre.


The solubility product of
AgCl
is
#$%
"!
".!24 "!

#B%
"!
".24 "!

#'%
"!
".&2 "!

#)%
"!
&.2 "!

/4.
"&
& /
2 "!
sp
K of Ag CrO is

. *hat happens when solutions of (!! ml of


(
"! M Ag
+
and 2!! ml of
&
/
(
"! M CrO ion

are mixed 3
#$% Precipitate will form #B% Precipitate will not form
#'% Precipitation starts #)% Precipitation cannot be predicted
/.. If sp
K of AgCl
is ta6en as
"! &
"! M

. *hat will be the solubility in !."M NaCl 3


#$%
"!
"!

#B%
8
"!

#'%
2
"!

#)%
/
"!

P$DD$EF-<II
/:. M + D + T are
#$%
&
+ + AgBr H S AgCl
#B%
( &
+ + AgNO NO AgCl
#'% ( )
& (
&
+ + Ag S Pb NO S
#)%
& & ( &
+ + Na S O H S S
/8. , + P + = are
#$%
( & / &
+ + AgNO Na SO Ag S
#B%
& & ( & / &
+ + Na S O Na SO Ag S
#'%
& /
+ + AgBr Na SO PbS
#)%
& /
+ + AgCl Na SO PbS
2!. 0 + W + < are
#$%
&
+ + PbS SO BaS
#B%
& & ( & /
+ + SO Ag S O BaSO
#'%
& & /
+ + Pb Cl H S BaSO
#)%
&
+ + AgCl H S BaS

P$DD$EF L-I-
Dtudy the following road map and answer question
2". The compound #-%+ #the ma5or product% is
#$%
Ph
OH
#B%
O
Ph
#'%
O
Ph
#)%
O
Ph
2&. The reagent C can be
#$% 1aeyers =eagent #B% 7ucas =eagent
Sri Chaitanya Page 9 Vizag

#'%
&
? I NaOH
#)% &+/)initrophenyl hydra9ine
2(. The product G is :
#$%
Ph
#B%
Ph
#'%
Ph
Cl
#)%
Cl
Ph
P$DD$EF L--
$ chemist opened a cupboard to find four bottles containing water solutions+ each of which had lost its
label. 1ottles "+ &+ ( contained colourless solutions+ while bottle / contained a blue solution. The labels
from the bottles were lying scattered in the floor of the cupboard. They were :
'opper #II% sulphate+ Hydrochloric acid
7ead nitrate+ Dodium carbonate
1y mixing samples of the contents of the bottles+ in pairs+ the chemist made the following observations.
1ottle " O 1ottle & *hite precipitate
1ottle " O 1ottle ( *hite precipitate
1ottle " O 1ottle / *hite precipitate
1ottle & O 1ottle ( 'olourless gas evolved
1ottle & O 1ottle / ,o visible reaction
1ottle ( O 1ottle / 1lue precipitate
2/. 1ottle ( contains
#$% copper #II% sulphate #1% hydrochloric acid
#'% lead nitrate #)% sodium carbonate
22. *hen bottle " is mixed with bottle /+ white precipitate is observed+ which is
#$% PbD0
/
#1% Pb'0
(
#'% Pb'l
&
#)% Pb#,0
(
%
&
24. *hich of the bottle will give distinctive deep blue colour with ,H
(
3
#$% 1ottle " #1% 1ottle & #'% 1ottle ( #)% 1ottle /
P$DD$EF --I
'onsider the following partially labelled figure for an ideal binary solution of ben9ene and toluene and
answer the following questions.
2.. *hat is
o
toluene
p
#&2
o
'% 3
#$% (! mm Hg #1% "!! mm Hg #'% &! mm Hg #)% /! mm Hg
2:. The composition of liquid for which the vapour contains equal number of ben9ene and toluene molecules
is nearly
#$%
toluene
- !...
#1%
toluene
- !.2&
#'%
toluene
- !.//
#)%
toluene
- !.&(
P$DD$EF --II
*hen a liquid is completely miscible with another liquid+ a homogeneous solution consisting of a single
phase is formed. If such a solution is placed in a close evacuated vessel+ the total pressure exerted by
vapour+ after the system attained equilibrium will be equal to the sum of partial pressures of the
constituents. $ solution is said to be ideal if its constituents follow =aoultIs law under all conditions of
concentrations i..e+ the partial pressures of each and every constituent is given by
o
i i i
p x p . *here p
i
is
Sri Chaitanya Page 10 Vizag

the partial pressures of the constituent i+ whose mole fraction in the solution is x
i
and
o
i
p is the
corresponding vapour pressure of the pure constituent.
The changes in the thermodynamic functions when an ideal solution is formed by mixing pure
components is given by the following expression.
mix total i i
i
E n =T x ln x

#"%
where n
total
is the total moles of all the constituents present in the solution.
mix total i i
i
D n = x ln x

#&%
mix total i i total i i
i i
H n =T x ln x n x ln x !

#(%
mix
W !
#/%
Dince both the components of an ideal binary liquid system follow =aoultIs law of the entire range of
the composition+ the partial pressure exerted by the vapours of these constituents over the solution will
be given by
o
$ $ $
p x p #2%
o
1 1 1
p x p #4%
where x
$
and x
1
are the mole fractions of the two constituents in the liquid phase and
o
$
p and
o
1
p are the
respective vapour pressures of the pure constituents. The total pressure #p% over the solution will be the
sum of the partial pressures. The composition of the vapour phase #y
$
% can be determined with the help of
)altonIs law of partial pressures
28. Jor an ideal solution in which
o o
$ 1
p p > + the plot of total pressure #p% versus the mole fraction of $ at
constant temperature in the vapour phase is
#$%

p
p
1
o
p
$
o
!
"

"
!

y
$
y
1
#B%

p
p
1
o
p
$
o
!
"

"
!

y
$
y
1
#'%

p
p
1
o
p
$
o
!
"

"
!

y
$
y
1
#)%

p
p
1
o
p
$
o
!
"

"
!

y
$
y
1
4!. $ plot of reciprocal of total pressure #"?p% #yaxis% versus y
$
#xaxis% gives
#$% a linear plot with slope Q
o o
1 $
" "
p p
_


,
#B% a linear plot with slope Q
o o
$ 1
" "
p p
_


,
#'% a linear plot with slope Q
o
1
"
p
#)% a linear plot with slope Q
o o
$ 1
p p
4". Two liquids $ and 1 form an ideal solution at temperature T. *hen the total vapour pressure above the
solution is 4!! torr+ the mole fraction of $ in the vapour phase is !.(2 and in the liquid phase !..!. The
vapour pressures of pure 1 and $ are
#$% :!! torrS "(!! torr#1% "(!! torr+ (!! torr #'% (!! torr+ "(!! torr #)% (!! torr+ :!! torr
P$DD$EF --III
$ssume that there were four possible values
" "
"+ + + "
& &
_
+ +

,
for the spin quantum number m
s
. Principal
quantum number n is defined as usual. However+ quantum number l and m+ are defined as follows:
l : " to #n O "% in integral steps m
l
: l?& to Ol?& #including 9ero+ if any% in integral steps The orbitals
corresponding to l Q "+ &+ (+ X designated as $+ 1+ ' .. respectively
4&. The number of elements that would be present in the second period of the periodic table is
#$% 8 #1% &! #'% &/ #)% (4
4(. If $ufbauIs principle is not violated i.e. #n O l% rule must be followed+ the outermost electronic
configuration of an element with atomic number "!! would be
Sri Chaitanya Page 11 Vizag

#$% (1
:
/$
/
#1% ('
"4
/$
:
#'% ('
"&
/1
:
#)% /1
"&
2$
:
4/. The number of suborbitals and the maximum number of electrons that can be filled in Forbitals are
respectively
#$% 4+ &/ #1% 2+ &! #'% .+ &: #)% cannot be determined
P$DD$EF --I<
$ liquid #$% #mol.wt "&!%has a normal boiling point of
!
4! C
.*hen a !.2g of solute #Mol.wt "(!%is
dissolved in &!g of $+ it shows an elevation in boining point of !.2! @. $nswer the following
42. The vapour pressure of the solution at
!
4! C
is nearly
#$% .2! mm #B% ./! mm #'% .(! mm #)% .&! mm
44. The molal elevation constant ( )
"
K molal

of liquid #$% is nearly


#$% ".4 #B% &.4 #'% (.4 #)% /.4
4.. If liquid #$% is to be distilled at
!
2! C
without decomposition+ what maximum pressure is to be maintained
in the flas6 nearly 3
#$% (/! mm #B% /.! mm #'% 2&! mm #)% 4/! mm
P$DD$EF --<
$ compound #$% given below is 6ept in acidic medium for sometime. It was observed that #$%
hydrolyses into #1% and #'%. The properties of #$%+ #1% ; #'% are tested with different reagents and
tabulated
O O
CH
3
CH
3
OH
O
4:. #1% formed is
#$%
O
O
OH
CH
3
#B%
O
O
CH
3
CH
2
OH
#'%
O
O
OH
CH
3
#)% 1oth $ ; 1
48. 'ompound #' % is :
#$%
( (
TT
O
H C C CH
#B%
( &
TT
O
H C CH C H
#'% HCHO #)%
(
H C CHO
.!. #1% is formed due to
#$% Hydrolysis followed by cleavage of ' 0 bond and followed by esterification between COOH and
OH group
#B% )ecarboxylation of COOH group
#'% 0xidation of
&
CH COOH
into COOH #)% 1oth $ and 1
P$DD$EF --<I
Sri Chaitanya Page 12 Vizag

$ pleasant smelling optically active ester #$% has molecular weight ":4. It does not react with in
. Hydrolysis of #$% gives two optically active compounds 1 and '. compound #'% gives positive iodoform
test and on warming with conc. gives ) #sayt9eff product% with no geometrical isomers. #'% on
treatment with ben9ene sulphonyl chloride gives #F% which on treatment with ,a1r gives optically active
J. *hen slat of #1% is treated with racemic mixture of J is formed
.". Dtructure ofcompound 1
#$% #B%
#'% #)%
.&. Dtructure of compound '
#$% #B% #'% #)%
.(. Dtructure of $ is
#$% #B%
#'% #)%
P$DD$EF --<II
Fpoxides #or oxiranes% are three membered cyclic ethers and differ from other cyclic and acyclic ethers in
that they are reactive to various reagents. The reason for this reactivity is the strained three membered ring.
=eactions with nucleophiles can result in ring opening and relief of strain. ,ucleophiles will attac6 either
of the electrophilic carbons present in an epoxide by an D
,
& reaction
./.
$ and 1 are
#$% #B%
#'% #)%
.2. The reaction of with =Mg- followed by hydrolysis leads to the formation of
Sri Chaitanya Page 13 Vizag

#$% #B% #'% #)%
P$DD$EF --<III
Hoffmann bromamide reaction involves conversion of a carboxylic acid amide into an amine with a loss of
a carbon atom on treatment with aqueous sodium hypobromite. Thus Hoffmann results in shortening of a
carbon chain
Mechanism of the reaction is :
.4.
#$% #B% #'% #)%
... *hich of the following will not give Hoffmann bromamide reaction
#$% #B% #'% #)%
.:.
#$% #B% #'% #)% ,one
P$DD$EF --I-
)icarboxylic acids contain two carboxylic acid groups. $cidity of carboxylic acid depends upon stability
of intermediate formed. The hydrogen present in carboxylic acid is labile. )icarboxylic acids on
decarboxylation form monocarboxylic acids+ al6anes and cyclic 6etones depending upon conditions.
Ereater the symmetry+ higher will be the melting point
.8.
Sri Chaitanya Page 14 Vizag

#$% omethyl acetophenone #B%
#'% #)%
:!. *hich of the following statements are correct :
i% bromo acids on decarboxylation give unsaturated hydrocarbons.
ii% of fumaric acid is lower than+ of maleic acid
iii% on reaction with gives corresponding anhydride
iv% on heating with gives a product which contain equal no. and bonds
#$% i+ii+ iii+ iv #B% ii+iii+ iv only #'% i + ii+ only #)% i+iii+ iv only
:". Pic6 up the correct statement from the following
i% 0n electrolysis of aqueous sodium formate liberates hydrogen gas both at cathode and anode
ii% $queous sodium salt of butane dioic acid on electrolysis gives Fthylene
iii% $queous sodium salt of Jumaric acid on electrolysis gives $cetylene
$queous sodium salt of "+4 hexane dioic acid on electrolysis give 'yclo butane as ma5or product
#$% i+ ii+ iii #B% ii+ iii+ iv #'% 0nly iii + iv #)% $ll are correct
Passage
A frost diagram of an element X is a plot of NE for the couple X(N)/X(0) against the oxidation
number, N of the element !he most stable oxidation state of an element in a"ueous solution corre
sponds to the species that lies lo#est in its frost diagram$ %rost diagrams can be used to gauge the
inherent stabilities of different oxidation states of an element and to decide #hether particular
species are oxidi&ing (or) reducing agents$ !he oxidi&ing agent in the couple #ith the more positi'e
slope (the more positi'e E ) is liable to undergo reduction$ !he reducing agent of the couple #ith
the less positi'e slope (the most negati'e E ) is liable to undergo oxidation$ A species in a frost
diagram is unstable #ith respect to disproportionation if its point lies abo'e the line connecting the
t#o ad*acent species$ !he species #ill tend to comproportionate into an intermediate species that lies
belo# the straight line *oining the terminal species$ %ollo#ing is the frost diagram of different
nitrogen compounds
Sri Chaitanya Page 15 Vizag

.
4
2
/
(
&
"
!
"
( & " ! O" O& O( O/ O2
,H
(
,
&
H
/
,H
&
0H
,0
(
,H 0H
+
& 2
, H
+
/
,H
+
&
,
&
, 0
,0
&
,0

& /
, 0
(
,0

basic
medium
&
, 0
&
H,0
& /
, 0
(
H,0
oxidation ,o
,FY
$cidic
medium
:&. 'hoose the correct statement
#$%
&
,
can be disproportionated into
&
,H 0H
and ,0
#B%
&
,0

can be disproportionated into ,0 and


& /
, 0
#'%
&
,H 0H
can not be disproportionated into
( &
,H ;,
#)%
(
,H 0H
+
can be disproportionated into
& 2
, H
+
ion and
&
,
:(. *hich of the following is the correct statement
#$% $mmonium nitrate can undergo disproportionation reaction in acidic medium
#B% $mmonium nitrate disporportionation has negative free energy change in acidic medium
#'% $mmonium nitrate can undergo comproportionate reaction in acidic medium
#)% $mmonium nitrate can not undergo comproportionate reaction in acidic medium
:/. 'hoose the correct statement
#$% potassium nitrite can undergo disproportionation into ,0 and
(
,0

in basic medium
#B% potassium nitrite can undergo disproportionation into ,0 and
& /
, 0
in acidic medium completely
#'% potassium nitrite can undergo disporportionation into ,0 and
& /
, 0
in acidic
medium incompletely #)% none of the above statements is correct
Passage
+ater can be thought of as h,drogen oxidi&ed b, ox,gen$ !hus h,drogen can be reco'ered b,
reduction of #ater, using an a"ueous solution of sodium sulphate, at a platinum electrode connected
to the negati'e terminal of a batter,$ !he solution near the electrode becomes basic$
+ater can also be thought of as ox,gen reduced b, h,drogen$ !hus, ox,gen can be reco'ered b,
oxidation of #ater at the -.t/ electrode connected to the positi'e terminal$
+hen copper is used at both electrodes gas is generated onl, at one electrode during the initial stage
of electrol,sis
Another species in solution that can be reduced is sodium ion$ !he reduction of sodium ion to
metallic sodium does not occur in a"ueous solution, because #ater is reduced first$
!he electrode potential is affected b, other reactions ta0ing place around the electrode$ !he
potential of the
12
3u /3u
electrode in a 0$400 5
12
3u
solution changes as ( )
1
3u 67
precipitates$
.recipitation of ( )
1
3u 67
begins at
p7 8 9$:9
(temperature 8 1;3,
<49
#
= 8 4$00>40 at 1;3)
1
]
<?$4@ <40
40 8 @$?1>40 log 9:00 8 A$@:419
:2. 1ased on the above observations+ connect the following half reactions with the standard reduction
potentials #in volts%
Sri Chaitanya Page 16 Vizag

a% reduction of copper ion ( )
&
'u
+
i% O!.(/
b% reduction of oxygen ii% &.."!
c% reduction of water iii% !.:(
d% reduction of sodium ion #,a
O
% iv% !.!!!
e% reduction of hydrogen ion v% O".&(!
#$% ai+ bii+ ciii+ dv+ eiv #B% ai+ bv+ cii+ diii+ eiv
#'% aI+ biii+ cii+ dv+ eiv #)% aI+ bv+ ciii+ dii+ eiv
:4. Dtandard =eduction potential for
( )
( )
( ) s
& s
'u 0H &e 'u &0H

+ +
#$% !./(" < #B% !.(("< #'% !.&(" < #)% !."("<
:.. =eduction potential of copper electrode at pH Q "
#$% O!.2" < #B% O!./"< #'% O!.&" < #)% O!.("<
Passage
0 0
0 0
& ( & ( (
&
$' 0 1J @ '0 'H I
". H ? H 0
4! ' "eq
&. Me0H? H
$ 1 '
+
+


Me0'
Me0'
#excess%
& (
@ '0

Ph 1r
( )
&eq
)
". H
(
'0
&
'
& (
'0 'H ? base
&. @
&
'0
(
Ph 1r
( )
&eq
F
[ ]
&
&
". ,a0H? H 0
&. H
(. H 0
+

J
::. How many aromatic rings are there in J
#$% / #B% 2 #'% 4 #)% .
:8. Jrom the following correct statement?s are
i% H$I is aromatic
ii% Jormation of 1 involved hydrolysis and addition L elimination reaction.
iii% H1I possess four intramolecular hydrogen bonds.
iv% H1I possess two intramolecular hydrogen bonds
#$% i+ ii+ iv #B% i+ ii+ iii #'% ii+ iv #)% i+ iii
8!. 'hoose correct statements
i% formation of H)I involved
&
D,
attac6
ii% formation of HFI involved claisen ester condensation and *illiam sonIs synthesis.
iii% formation of HFI involved claisen ester condensation but not *illiam sonIs synthesis.
iv% HJI can give test with TollenIs reagent
#$% i+ iii #B% ii+ iv #'% i+ ii #)% i+ ii+ iv
Passage
!he formation of the oxide
x ,
5 6
per mole of
1
6
consumed is #ritten as
( ) ( )
x , s 1 g
1x 1
5 26 5 6
, ,

!he free energ, change of the reaction is gi'en b, BC 8 B7< !BD$


Ef the enthalp, change B7 and entrop, change BD are assumed to be independent of temperature,
the plot of BC 'ersus ! is linear such as sho#n in the follo#ing figure 0no#n as Ellingham
diagram$ %igure is #idel, used to discuss the principle in'ol'ed in the extraction of metal from its
oxide
Sri Chaitanya Page 17 Vizag

!he reduction of
x ,
5 6
b, carbon at ! F G0:3 ma, be represented as
x ,
1 1x
5 6 2 13 52 136
, ,

!he free energ, of this reaction can be obtained from the follo#ing
t#o reactions$
S
1 x , 4
1x 1
526 5 6BC
, ,

S
1 1
1326 136BC
8". 'hoose the correct statement
#$% The slope of linear plot of
E versus T
is positive for
x y
M 0
with the exception when HMI is carbon
#B% The slope of linear plot of
E versus T
is negative for
&
'0
#'% The slope of linear plot of
E versus T
is positive for '0
#)% The slope of plots of
E versus T
for the various oxides formed from
( )
( )
( ) s
M or M
l
are negative
8&. 'hoose correct statements from the following statements
i% The slope of
E versus T
plot becomes more positive when the oxide is formed from M#g%
ii% $t T .!: ' < + the stable oxide of H'I is
&
'0
where as at T .!: ' > + the stable oxide is '0.
iii% Mercury #II% oxide decomposes spontaneously to its elements by heating alone.
iv% =eduction of Gn0 by '0 starts at 4!! '
#$% i+ ii+ iii+ iv #B% i+ ii+ iv #'% ii+ iii+ iv #)% i+ ii+ iii
8(. 'hoose correct statements from the following
i% Jor the reduction of
x y
M 0
by H'I Uto be spontaneousV
" &
E E <
ii% decreasing ease of reduction of metal oxides by carbon is

& ( & (
Je0 Gn0 'r 0 Mg0 $l 0 'a0 > > > > >
.
iii% decreasing ease of reduction of metal oxides by carbon is

& ( & (
Je0 Gn0 $l 0 'r 0 Mg0 'a0 > > > > >
.
iv% =eduction of
& (
'r 0
by $l is possible at all temperatures
#$% i+ iv #B% ii+ iii #'% ii+ iv #)% iii+ iv
Passage :
Sri Chaitanya Page 18 Vizag

0
,ph
&
'00H
& 2
& &
' H 0H? H
". Do'l #i% @0H#'onc% ? H 0?
&. Me'd'l
#ii% H
$ 1
+
+


( ) ( )
& & & / &
'l'H '0 Ft ". 0H ? H 0 @Mn0 ". 0H ? H 0 Ft0H? H'l Ft0 ? Ft0H
Ft0,a excess &. H excess &. H ?
' ) F J E H

+ +


&
&
". ,H 0H ". MeIexcess
&. H ? ,i &. $g0H
I > @ 7 M

+
Ma5or Minor
8/. *hich of the following are correct statements
i% Decond step in the formation of H$I+ involved addition reaction only.
ii% I
st
step in the formation of H1I is a second order reaction.
iii% Jormation of H'I is a 9ero order reaction.
iv% Jormation of H'I is involved a tetrahedral transition state and formation of H'I is due to nucleophilic
addition and elimination
#$% i+ ii #B% ii+ iv #'% ii+ iii #)% i+ iv
82. 'hoose correct statements w.r.t formation of ) from ' and formation of H from E
#$% formation of H)I from ' is involved nucleophilic addition and internal nucleophilic substitution and
formation of H from E is $ldol condensation
#B% formation of H)I is involved nucleophilic addition only and formation of HHI from HEI is involved
internal 'laisen ester condensation
#'% formation of H)I from H'I is involved nucleophilic addition and internal *illiamsonIs synthesis and
formation of H from E is internal 'laisen ester condensation
#)% formation of H)I from H'I is involved nucleophilic substitution only and formation of HHI from HEI is
)iec6mannIs reaction
84. 'hoose incorrect statements
#$% HMI is thermodynamically more stable #B% H7I is thermodynamically less stable
#'% second step in the formation of HII from HHI is involved a cyclic transition state
#)% H>I is possessing two chiral centres
Passage
3onsider the follo#s reaction
( ) ( )
& / &
& N O g NO g
!he free energ, of the reaction occurring at 1?: 0 and 4atm has been plotted against the fraction
of
& /
N O
dissociated as sho#n ad*acent
8.. *hen two moles of ,0
&
change in to equilibrium mixture with
& /
N O
the
!
G is
#$% 2./! kJ #B% 2./! 6> + #'%
4.&/ 6>
#)% 4.&/ 6>
8:. *hen one mole of
& /
N O
change into equilibrium mixture with
&
NO
+ The
!
G is
Sri Chaitanya Page 19 Vizag

#$% 2./! 6> #B% !.:/ 6> #'% !.:/ 6> #)% 4.&/ 6>
88. Mar6 out the correct statements
#$% The conversion of
& /
N O
into &,0
&
is spontaneous
#B% The conversion of
&
&NO
into
& /
N O
is nonspontaneous
#'% The attainment of equilibrium from
& /
N O
and from
&
NO
both are equally spontaneous
#)% The attainment of equilibrium from& moles of
&
NO
with
& /
N O
is more spontaneous than the
conversion of
&
&NO
into
& /
. N O
Passage
C
(Resolvable)
HBr, ero!"#e
$ (C
%
H
11
Br)
&e'olo(r"se Br
2
)a*er
an# 'anno* be resolve#
HBr
B
( Non-resolvable)
a s"n+le oss"ble ro#('*
& (C
%
H
12
)
O
3
,-n,H
2
O
-n, Hea*
CH
3
C CH
3
O
al'. KOH
HBr,R
2
O
2
/ F
non-resolvable
Resolvable
(/!'ess)
0
"!!. 0rganic compound H$I is
C H
2
B r
B r
B r
C H
2
B r
a )
b )
' )
# )

"!". The resolvable organic compound H'I is
CH
2
Br
Br
Br
Br
Br
Br
Br
Br
a)
b)
')
#)
"!&. The resolvable organic compound+ E is
a) b)
') #)
CH
3
CH
3
CH
3
CH
3 CH
3
CH
3
CH
3
CH
3
CH
3
CH
2
CH
3
CH
2
CH
3
CH
2
Br
CH
2
Br
Br
Br
Br
Br
H
H
CH
H
H
H
H
Br
Br
Passage :
'ompound - is a trisaccharide which occurs principally in cottonseed meal. 'ompound - does not react
with 1endictIs or JehlingIs solutions nor does it mutarotate. $cid catalysed hydrolysis gives three
different )hexoses+ $+ 1 and '. 'ompounds $ and 1 as well as compound given below#figure "%+ all give
the same osa9one upon reaction with excess acidic phenylhydra9ine.
Sri Chaitanya Page 20 Vizag

CH1O
HO
H
HO
OH
OH
H
H
H
CH
2
OH
CH1O
H OH
CH
2
OH
F"+-1
&-0l2'eral#eh2#e
'ompound ' reacts with nitric acid to give optically inactive compound ). The @iliani Jischer approach
is used to establish the configurational relationship between )glyceraldehyde and '. The intermediate
aldotetrose which leads to ' does not give a meso compound when oxidi9ed by nitric acid. *hen $ is
treated with nitric acid+ the dicarboxylic acid # aldaric acid % produced is optically active. 1oth $ and 1
react with 2 moles of
/
HIO
. 0ne mole of $ gives 2 moles methanoic acid and one mole of methanal while
one mole of 1 gives ( moles of methanoic acid.+ & moles of methanal and one mole of carbon dioxide.
1oth $ and 1 are related to the same aldotetrose which is the diastereomer of the one to which ' is
related. Methylation of - followed by hydrolysis gives a &+ (+ /tri0 methyl)hexose #F% # derived
from $%+a "+(+/+4+tetra0methyl)hexose#J%#derived from 1% + and a &+(+/+4+tetraomethyl)hexose
#E% # derived from '%
"!(. 0bserve the following molecules
CHO
HO H
HO
OH
OH
H
H
H
CH
2
OH
CHO
HO
OH
OH
H
H
H
CH
2
OH
CHO
HO
OH
OH
H
H
H
CH
2
OH
CHO
HO H
HO
OH
H
H
CH
2
OH
CHO
HO
OH
O
H
H
CH
2
OH
CHO
HO
HO
OH
H
CH
2
OH
3
33
333
34
4 43
H OH
H OH
HO H
H
OH
O
'hoose the correct match :
#$%
+ + A III B V C I
#B%
+ + A I B VI C VI
#'%
+ + A III B IV C I
#)%
+ + A III B V C IV
"!/. How many moles of acetic anhydride are consumed to ma6e $ completely acetylated3
#$% ( #B% / #'% 2 #)% 4
"!2. The trisaccharide HxI is
#$% #B%
Sri Chaitanya Page 21 Vizag

#'% #)%
P$DD$EF
$n efflorescent salt is one that loses water to the atmosphere. This will occur if the water vapour
pressure in equilibrium with the salt is greater than the water vapour pressure in the atmosphere. Jor
example +
/ &
.2 CSO H O
could be efflorescent as it loses & molecules of
&
H O
and simultaneously forms
" formula unit of
/ &
.( CSO H O
.
( ) ( ) ( )
/ & / & &
.2 .( & CSO H O soli! CSO H O soli! H O gas +
If partial pressure of
&
H O
# let it be x torr% is less than the vapour pressure of water at the same
temperature it doesnIt mean
/ &
.2 CSO H O
will always effloresce. 0nly in that condition+ when the
partial pressure of moisture in the air is less than HxI. In other words+ this will occur when the relative
humidity is less than
&(.:
"
# The vapour pressure of water at &2
!
' is &(.: Torr%
'onversely+ it can be said that 'uD0
/
. (H
&
0 can reduce the moisture content of any confined volume of
gas to H
"
I torr
"!4. ( ) ( ) ( )
/ & / & &
.2 .( & CSO H O s CSO H O s H O g +
Jor the equilibrium+
p
K
at
!
&2 C is
/
".!:4 "!

atm
&
. Then which of the following is the appropriate
relative humidity at which ( )
/ &
.2 CSO H O s
will effloresce essentially3
#$% &".&2N #B% (2.(N #'% (8.4.N #)% 2!N
"!.. ( ) ( ) ( )
& / & & / &
."! "! Na SO H O s Na SO s H O g +
SPH
&
0Q
(
(.4/ "!

Jor the equilibrium+


&2 "!
/.!: "! .
p
K atm


If the vapour pressure of water at !
!
' is /.2: Torr+ at which
relative humidities will
& /
Na SO
be deliquescent #absorb moisture% when exposed to the air at !
!
'
essentially3
#$% &".&2N #B% (2.(N #'% 2!N #)% .!N
"!:. Fquilibrium constants are given for the following reactions at !
!
'
( ) ( ) ( )
"& /
& & & & &
.4 .& / S 4.:8 "!
p
AB H O s AB H O s H O g K atm

+
S
(
&
".4& "! PH O


( ) ( ) ( )
( ) ( )
"( 2 (
& & & & & &
&2 "! (
& & & & &
."& .. 2 S 2.&2 "! S (./88. "!
."! "! S /.!: "! (.4/ "!
p
p
M N H O s M N H O s H O g K atm PH O atm
P N H O s P N s H O K atm PH O atm


+
+

*hich one is most effective drying agent at !


!
' # The vapour pressure of
&
H O
at !
!
' is /.2: Torr%3
#$%
& &
.& AB H O
#B%
& &
.. M N H O
#'%
&
P N
#)% $ll are equally effective
P$DD$EF
$ chemist opened a cubboard to find four bottles containing water solutions+ each of which had lost its
label. 1ottle "+ & and ( contained colourless solutions+ while bottle / contained a blue solution. The
labels from the bottles were lying scattered on the floor of the cupboard. They were:
'oper #II% sulphate Hydrochloric acid
7ead nitrate Dodium carbonate
1y mixing samples of the contents of the bottles+ in pairs+ the chemist made the following observation:
Sri Chaitanya Page 22 Vizag

1ottle " 1ottle & *hite pecipitate
1ottle " 1ottle ( *hite pecipitate
1ottle " 1ottle / *hite pecipitate
1ottle & 1ottle ( 'olourless gas evolved
1ottle & 1ottle / ,o visible reaction
1ottle ( 1ottle / 1lue prec
+
+
+
+
+
+ ipitate
"!8. 1ottle ( contains
#$% copper #II% sulphate #B% hydrochloric acid
#'% lead nitrate #)% sodium carbonate
""!. *hen bottle " is mixed with bottle /+ white precipitate is observed+ which is
#$%
/
PbSO
#B%
(
PbCO
#'%
&
PbCl
#)% ( )
(
&
Pb NO
""". *hich of the following bottle will give distinctive colour with
(
NH
3
#$% 1ottle " #B% 1ottle & #'% 1ottle ( #)% 1ottle /
Passage
Ideal gas equation is represented as P<Qn=T. Eases present in universe were found to exhibit
ideal or nearly ideal behavior in the 1oyle temperature range only. They deviate from ideal gas
behavior at high pressure and low temperature. The deviations are explained in terms of
compressibility factor G. Jor ideal behavior GQ P<? n = T Q". The main cause to show deviations
were due to wrong assumptions made about forces of attraction and volume occupied by the
molecules. < in P< Q n = T is supposed to be volume of gas or the volume of the container in
which the gas is placed assuming that gaseous molecules do not have appreciable volume.
$ctually volume of the gas is that volume in which a gas molecule can move freely. If volume
occupied gas molecules is not negligible+ then the term < should be replaced by an ideal volume
which is available for free motion of each moleculeof the i.e for " mole of gas <
actual
Q volume of
the container L volume occupied by the moleculesQ<b
*here b represents the effective volume or 'ovolume or excluded volume occupied by the
molecules present in one mole of gas. <
actual
Q <nb # for nmoles of gas%. The excluded volume
can be calculated by considering bimolecular collisions. The excluded volume is the volume
occupied by the sphere of &r for each pair of moleculeQ#/?c% Z#&r%
(
Q /x: Zr
(
?(
The excluded volume for a single molecules is #&?c%xx: Zr
(
.Q /x#/?c% Zr
(
Q /<.
Therefore the excluded volume for , molecules is Q/,<Q/b #,<Qb%
T
c
+ P
c
and <
c
are critical constants of a gas. P
c
Q a?&.b
&
a is van der waalIs constant+ which is
elated to attractive forces. T
c
Q :a?&.=b <
c
Q(b
""&. *hich of the following statements are correct3
"% 7arger the value of T
c
? P
c
for a gas larger would be its excluded volume
&% 7arger is the excluded volume of gas + more will be its critical volume#<
c
%
(% The slope for an isochore obtained for a gas showing p#<b% Q=T is #=?<b%
/% The excluded volume for He is more than hydrogen
#$% "+&+( #B% "+&+/ #'% &+(+/ #)% (+/
""(. $s the pressure approaches 9ero i.e at very low pressures+ the curves plotted between G and P for n
moles of gases have the following characteristics
"% The intercept on yaxis lead to the value of unity
&% The intercept on yaxis lead to a value of HnI
(% The curves possess same slope for different gases at the same temperature
/% The curves possess different slopes for different gases at the same temperature
Sri Chaitanya Page 23 Vizag

2% The curves possess same slope for a gas at different temperature
#$% "+ /+2 #B% &+( #'% &+(+/ #)% &+(+2
""/. The ratio of coefficient of thermal expansion [Q#d<?dT%
p
?< and the isothermal compressibility
@Q #d<?dP%
T
?v for an ideal gas is
#$% LP?T #B% P?T #'% T?P #)% LT?P
Passage
Primary amines react with nitrous acid to form dia9onium cation. It is an unstable specires and converts
into carbo cation
""2. *hich of the following will be least stable 3
#$% 'H
(
'H
&

O
,

, #B% '
4
H
2

O
,

,
#'% 0'H
(
!'
4
H
/

O
,

, #p% #)% 0
&
,'
4
H
/

O
,

, #p%
""4. In the given reaction : 'yclobutylaminomethane O ,a,0
&
O H'l product
#$% cyclobutylmethanol #B% cyclopentanol
#'% chlorocyclopentane #)% $ll these
"".. *hich daia9onium cation is most reactive for coupling reaction
#$% '
4
H
2
,
&
O
#B% 'H
(
L'
4
H
/
,
&
O
#p%
#'% 0
&
,'
4
H
/
,
&
O
#p% #)% 'H
(
0'
4
H
/
,
&
O
#p%
P$DD$EF :
)issociation of wea6 of electrolyte is expressed in terms of 0stwald dilution law. $n acid is
substances that furnishes a proton or an electron pair acceptor. *here as a proton acceptor or
electron pair donoris a base. Dtrong acid has wea6 con5ugate base. The dissociation constants of
an acid #@
a
% and it s con5ugate base #@
b
% are related by @
w
Q@
a
x @
b
. pH Op0H Q"/.1uffer solution
donIt show appreciable change in when a few drops of acid or base is added.
$nswer the following questions:
"":. *hich of the following statements are correct3
"% pH of "!
"!
molar ,a0H is nearly .
&% the degree of dissociation is given by "? "O "!
p6aPh
(% Jor wea6 electrolytes of polyprotic acid nature having no other electrolyte + the anion
concentration produced in second step of dissociation is always equal to @
&
at reasonable
concentration of acid
/% The concentration of amide ions produced during self ioni9ation of ammonia is equal to
concentration of ammonium ions
2% 0stwald dilution law is valid for strong electrolytes
#$% "+&+( and 2 are correct #B% "+&+(+and / are correct
#'% "+(+/+and 2 are correct #)% &+(+/+and 2 are correct
""8. *hich of the following statements are true 3
"% Perchlorate ion is a wea6er base than chlorate ion
&% The degree of dissociation of water is ".: x"!
8
(% the equilibrium constant for dissociation of water is "..: x"!
"4
/% phosphate ion is con5ugate acid of monhydrogenphosphate ion
#$% "+&+and ( are correct #B% &+ ( and / are correct
#'% "+ & and / are correct #)% " and & are correct
"&!. !."4gm of hydra9ine @
b
Q/x"!
4
are dissolved in water and the total volume of solution is made
upto 2!!ml. The percentage of hydra9ine that reacts with water is
#$% &N #B% (N #'% /N #)% "N
Sri Chaitanya Page 24 Vizag

P$DD$EF :
F
&
reaction is bimolecular reaction. F
&
reaction is of two types . Hoffmann elimination end
Dayt9eff elimination
' ' O1:
' ' ' ' ' ' 'Q' O1H
O
O7

H
+
1

H
+
H
H
+

+
#
#
#

I
II
III
#

H
$nswer the following questions based on the above mechanism
"&". In F
&
reaction formation of Hoff amnn product ta6es place by formation of which intermediate
#TD% 3
#$% I #B% II #'% III #)% I and III
"&&. *hich one of these compounds will give Dayt9eff product in F
&
reaction3
#$% 'H
(
'H
&
'H#1r%'H
(
#B% 'H
(
'H
&
'H#J%'H
&
'H
(
#'% 'H
(
'H
&
'H
&
L,
O
#'H
c%(
0H

#)% 'H
(
'H
&
'H#0'0'H
c%
'H
(
"&(. In F
&
reaction Ts has character
#$% al6ene #B% 'arbonium ion #'% carbanion #)% any othese
P$DD$EF :
$n aqueous solution of salt #$% gives white crystalline precipitate #1% with ,a'l solution. The filtrate gives a
blac6 ppt. #'% when H
&
D is passed in it. 'ompound #1% is dissolved in hot water and the solution gives a yellow
ppt. #)% on treating with ,aI and cooling. The compound #$% does not give any gas with dil.
H'l but liberated reddish brown gas on heating
"&/. The compound #$% in the above passage is
#$% Pb#,0
(
%
&
#B% PbD #'% 'u#,0
(
%
&
#)% ,a'l
"&2. The compound #'% in the above passage is
#$% ,aI #B% PbD #'% Pb0 #)% Pb'l
&
"&4. The compound #)% is
#$% PbI
&
#B% Pb0 #'% PbD #)% ,0
&
P$DD$EF
$ll the four colligative properties of solutions depend solely on the total number of solute particles present in
solution. <arious electrolytes ioni9es and yield more than one particle per unit in solution. The properties
of these electrolytes can be correlated by the use of a factor called vanIt Hoff factor #i%
"&.. The vanIt Hoff factor for ,a'l is ".8. The degree of dissociation is
#$% /2N #B% "!!N #'% 8!N #)% 4!N
"&:. $ !.!" M solution of @
(
Je #',%
4
is 2!N dissociated at &.
!
'+ then the osmotic pressure of solution will be
#$% !.!& atm #B% !.4" atm #'% !..: atm #)% ".&8 atm
"&8. The ratio of the elevation of boiling point for ,a'l solution to that for sugar of same concentration is
#$% " #B% & #'% ( #)% !.2
P$DD$EF
$ solution which remains in equilibrium with undissolved solute+ in contact+ is said to be saturated. The
concentration of a saturated solution at a given temperature is called solubility. The product of concentration of ions
in a saturated solution of an electrolyte at a given temperature+ is called solubility product #@
DP
%. Jor the electrolyte
$
x
1
y
with solubility D+
$
x
1
y
#s% x$
yO
O y1
x
*hile calculate the solubility of a sparingly soluble salt in the presence of some strong electrolyte containing a
common ion+ the common ion concentration is practically equal to that of strong electrolyte. If in a
Sri Chaitanya Page 25 Vizag

solution+ the ionic product of an electrolyte exceeds its @
DP
value at a particular temperature+ then
precipitation occurs
"(!. The solubility of PbD0
/
in water is !.!(!( g%l at &2
!
'+ its solubility product at that temperature is
#$% "!
/
M
&
#B% 8.": x "!
/
M
&
#'% "!
:
M
&
#)% 8.": x "!
:
M
&
"(". The solubility of 1aD0
/
in !." M 1a'l
&
solution is #@
DP
of 1aD0
/
Q ".2 x "!
8
%
#$% ".2 x "!
8
M #B% ".2 x "!
:
M #'% &.&2 x "!
"4
M #)% &.2 x "!
":
M
"(&. If D
!
+ D
"
+ D
&
and D
(
are the solubilities of $g'l in water+ !.!"M 'a'l
&
+ !.!" M ,a'l and !.!.2 M $g,0
(

solutions respectively+ then
#$% D
!
B D
"
B D
&
B D
(
#B% D
!
B D
&
B D
"
B D
(
#'% D
!
B D
"
Q D
&
B D
(
#)% D
!
B D
&
B D
(
B D
"
P$DD$EF
$ metal complex having composition 'r#,H
(
%/1r
&
I was isolated in two forms #-% and #C%.
Jorm #-% reacts with $g,0
(
to give a pale yellow precipitate which is partially soluble in excess of ,H
/
0H
whereas #C% gives a greenish yellow precipitate which is insoluble in ,H
/
0H
"((. Delect the correct statement
#$% The formula of #-% and #C% are
( ) [ ] Br IBr NH Cr
/ (
and
( ) [ ]
( & ( (
NH I Br NH Cr
respectively
#B% The formula of #-% and #C% are U'r#,H
(
%
/
I1rV 1r and U'r#,H
(
%
/
1r
&
V I respectively
#'% The formula of #-% and #C% are both U'r#,H
(
%
/
IV1r I
#)% The formula of #-% and #C% are U'r#,H
(
%
(
I1r
&
V #,H
(
%
&
"(/. 1oth the #-% form and #C% form show
#$% lin6age isomerism #B% coordination isomerism
#'% Ioni9ation isomerism #)% none of these
"(2. Delect the correct statement
#$% #-% L cis form optically inactive+ #C% L cis form optically active
#B% #-% L cis form optically inactive+ #C% L trans form optically active
#'% The cis and trans forms of both - and C are optically active
#)% The cis and trans form of both - and C are optically inactive
P$DD$EF :
$n optically active compound #$%
: "&
C H
gives an optically inactive compound #1%
: ":
C H
on
hydrogenation. #$% gives no precipitate with
( &
# % Ag NH
+
and gives optically inactive #'%
: "/
C H
with
&
H in
presence of ,ic6el 1oride
"(4. 'ompound #1% is
#$%
( & & & & (
(
T
CH CH CH CH CH CH CH
CH

#B%
( & 4 (
# % CH CH CH
#'%
( & & & & (
(
T
CH CH CH CH CH CH CH
CH

#)%
( & & & 2
( (
T T
CH CH CH CH C H
CH CH

"(.. 'ompound #$% is
#$%
( (
(
T
CH CH CH CH C C CH
CH

#B%
( & (
(
T
CH C CH CH C C CH
CH


#'%
( & & (
CH CH CH CH CH C C CH
#)%
(
( (
T T
CH C CH CH C CH
CH CH

"(:. 'ompound #'% is
#$%
( & (
(
T
CH C CH CH CH CH CH
CH

#B%
( (
(
T
CH CH CH CH CH CH CH
CH


Sri Chaitanya Page 26 Vizag

#'%
( & & (
CH CH CH CH CH CH CH CH
#)%
( &
( (
T T
CH C CH CH CH CH
CH CH

P$DD$EF :
$ yellow coloured powder #$% reacts with acetic acid to form a white crystalline solid #1% which is used
for curing s6in diseases. 'omp #1% on heating gives solid #$%+ a gas #'% and a compound #)%. comp.#)% on
reacting with
&
I and
& (
Na CO
forms a yellow precipitate of compound #F%. comp. #1% when treated with a
solution of sodium carbonate gives a white ppt. of #J% and when
&
H S is passed into solution of #1%+ it
forms a blac6 ppt+ of #E%
"(8. Identify #)%
#$%
( & (
CH CH COCH
#B%
(
CH COOH
#'%
( (
CH COCH
#)% PbO
"/!. 'ompound #$% is
#$% PbO #B%
/
PbCrO #'% MnS #)%
& /
Na CrO
"/". The white ppt. #J% is
#$%
/
NH Cl #B% &nS #'%
& 4
U # % V Ca 'e CN
#)%
( &
& . # % PbCO Pb OH
P$DD$EF
$ neutral compound #$%+
8 "4 &
C H O
gives
2 : &
#1% C H O
and
/ "!
#'% C H O
on refluxing with dil. $l6ali
followed by acidification. #1% liberates
&
CO from saturated sodium bicarbonate solution. 'ompound #'%
on dehyration yields &1utene as the ma5or product. 'ompound #1% on treatement with osmium tetraoxide
followed by reductive hydrolysis gives #)%+
2 "! /
C H O
"/&. 'ompound #)% when treated with lead tetra acetate furnishes acetone and #F%
& & (
C H O
. #F% is acidic and
reduces tollenIs reagent compound. #)% is
#$%
( &
T T
CH CH CH CH COOH
OH OH

#B%
( &
T T
CH CH CH CH COOH
OH OH


#'%
( &
T T
CH CH CH CH OH
COOH OH

#)%
(
(
T
T T
CH
CH C CH COOH
OH OH

"/(. 'ompound #1% is
#$%
(
(
T
CH C CH COOH
CH

#B%
( &
CH CH CH CH COOH

#'%
(
T
CH CH CH CH CHO
OH

#)%
( &
T T
CH CH CH CH CH
OH OH

"//. 'ompound #$% is
#$%
( (
( & (
T TT T
CH O CH
CH C CH C O CH CH CH
#B%
( & & & & (
TT
O
CH CH CH CH C O CH CH CH CH

#'%
(
( & & & (
T TT
CH O
CH C CH C O CH CH CH CH

#)% ,one of these
Sri Chaitanya Page 27 Vizag

P$DD$EF
$ waxy crystalline solid #$% with garlic odour is obtained on burning a white solid #F% in stream of air. #$%
reacts vigorously with hot water giving a gas #1% and an acid #'%. Eas #1% has unpleasant odour of rotten
fish and is neutral towards litmus. *hen gas #1% is passed through a blue solution of compound#J% it
produces a blac6 precipitate of compound #)%. 'ompound #J% gives chacolate color ppt. 0f #E% with
[ ]
/ 4
# % K 'e CN
"/2. 'ompound #E% is
#$% [ ]
/ 4
# % 'e 'e CN
#B%
/
CSO #'% [ ]
& 4
# % &n 'e CN
#)% [ ]
& 4
# % C 'e CN
"/4. The gas #1% is
#$%
(
NH
#B%
(
PH
#'%
&
SO #)%
(
SO
"/.. The acid #'% is
#$%
& /
H SO #B%
( /
H PO
#'% HCl #)%
( &
H PO
Passage :
$l6yl derivatives of aceto acetic ester can undergo two types of hydrolysis+ 6etonic and acid hydrolysis.
The scheme of these hydrolysis reactions are as follows.
=etonic h,drol,sis
( ) ( )
( )
& /
" .
( & 2 ( & & &
KOH !il
H SO
CH COCH(COOC H CH CH ( CO )tOH + + C
33
O
Acid h,drol,sis
.
( & 2 (
Con* KOH
CH COCH(COOC H CH COOK (CHCOOK )tOH + +
The above names are in agreement to the types of products obtained
"/:. *hat is the final product D in the given reaction
( ) ( )
( )
( /
" "
( & & 2 &
)tONa mole KOH )tI
H PO
CH COCH COOC H P + S
#$%
(
CH COOH
#B%
( & & (
CH CH CH CH C
33
O

#'%
( (
(
CH CH C CH
33 3
O CH
#)%
(
CH )t C
33
O
"/8. *hich reaction sequence can prepare succinic acid as final product
#$%
( )
&
0
"
( &
)tONa e, Cl CH COO)t KOH
H
CH COCH COO)t
+

#B%
( )
&
0
"
( &
)tONa e, Cl CH COOH KOH
H
CH COCH COO)t
+

#'%
( )
&
" .
( &
)tONa e, Cl CH COOMe Con* KOH
CH COCH COO)t


#)%
( ) " .
( & (
)tONa e, Con* KOH
CH COOCH COO)t CH Cl C
33
O
"2!.
The final product is
#$%
( & (
CH CH CH C C
33 33
O O
#B%
(
CH OH C
33
O

#'%
( &
CH CH COOH C
33
O
#)%
( & & (
CH CH CH CH C C
33 33
O O
Passage :
Sri Chaitanya Page 28 Vizag

$ system of greater disorder of molecules is more probable. The disorder of molecules is reflected by
the entropy of the system. $ liquid vapori9es to form a more disordered gas. *hen a solute is present+
there is additional contribution to the entropy of the liquid due to increase randomness. $s the entropy
of solution is higher than that of pure liquid+ there is wea6er tendency to form the gas. Thus+ a solute
#non volatile% lowers the vapour pressure of a liquid+ and hence a higher boiling point of the solution.
Dimilarly+ the greater randomness of the solution opposes the tendency to free9e. In consequence+ a
lower the temperature must be reached for achieving the equilibrium between the solid #fro9en solvent%
and the solution. Flevation of 1.Pt ( )
b
-
and depression of J.Pt ( )
f
-
of a solution are the colligative
properties which depend only on the concentration of particles of the solute+ not their identify. Jor dilute
solutions+
b
-
and
f
-
are proportional to the molality of the solute in the solution.
b b
- K m
b
K
Q Fbullioscopic constant Q
&
"!!!
o
b
.ap
(- M
H
$nd
f
-
Q
f
K m

f
K
Q 'ryoscopic constant Q
&
"!!!
o
f
fs
(- M
H
#M Q molecular mass of the solvent%
The values of
b
K
and
f
K
do depend on the properties of the solvent. Jor liquids+
!
.ap
b
H
-

is almost
constant .UTroutanIs rule+ this constant for most of the unassociated liquids #not having any strong
bonding li6e Hydrogen bonding in the liquid state% is equal to 8! >?mol.V
Jor solutes undergoing change of molecular state is solution #ioni9ation or association%+ the observed T
values differ from the calculated ones using the above relations. In such situations+ the relationships are
modifies as
b b
- iK m
S
f f
- iK m
*here i Q <anItHoff factor+ greater than unity for ioni9ation and smaller than unity for association of
the solute molecules
"2". )epression of free9ing point of which of the following solutions does represent the cryoscopic constant
of water3
#$% 4N by mass of urea is aqueous solution #B% "!!g of aqueous solution containing ":g of glucose
#'% 28g of aqueous solution containing 8g of glucose
#)% " M glucose solution in water
"2&. )issolution of a nonvolatile solute into a liquid leads to the
#$% )ecrease of entropy #B% Increase in tendency of the liquid to free9e
#'% Increase in tendency to pass into the vapour phase
#)% )ecreases in tendency of the liquid to free9e
"2(. To aqueous solution of ,aI+ increasing amounts of solid
&
HgI
is added. The vapour pressure of the
solution
#$% decreases to a constant value #B% increases to a constant value
#'% increases first and then decreases
#)% remains constant because
&
HgI
is sparingly soluble in water.
Passage
*erner performed two experiments as given below Fxperiment ": He prepared a compound #x% by
reacting @'l with
/
PtCl
. The compound #x% did not give any precipitate with
(
AgNO
but gave electrical
conductance corresponding to ( ions.
Fxperiment &: He too6 !.("8 g of
( &
.4 CrCl H O
and passed through a cation exchange resin and the acid
coming out required &!.2 ml of !."&2 M ,a0H
"2/. The correct formula of the compound #x% is
Sri Chaitanya Page 29 Vizag

#$% [ ]
&
KPtCl Cl
#B [ ]
& /
K PtCl
#'% [ ]
& 4
K PtCl
#)% [ ]
/
K PtCl
"22. The number of moles of $g'l which will be precipitated with
(
AgNO
which will be precipitated with
(
AgNO
in
(
CrCl
.
&
4H O
is
#$% & #B% ( #'% " #)% !
"24. The complex
(
CrCl
.
&
4H O
can be rightly represented as
#$% ( )
& &
/
Cr H O Cl Cl 1
]
#B% ( )
& ( &
(
.( Cr H O Cl H O 1
]

#'% ( )
& (
4
. Cr H O Cl 1
]
#)% ( )
& &
2
Cr H O Cl Cl 1
]
P$DD$EF
$n octahedron can be drawn within a cube by choosing the centre of its six faces. The centre of cube
constitutes an octahedral void. In close pac6ing two anions touch each other along the line obtained
by 5oining the centres of two ad5oining face and one cation #occupying an octahedral void% and two
anions #occupying at the centre of two opposite faces% touch each other along the line 5oining the
centres of two opposite faces
"2.. The ratio of
? r r
+
for the above passage is
#$% !.&&2 #B% !..(& #'% !./"/ #)% "
"2:. The coordination number of atom present in the void formed in the above passage is
#$% / #B% 4 #'% ( #)% "&
"28. The number of octahedral voids present in &(/g of ,a'l is
#$% ,
$
#B% / ,
$
#'% "4,
$
#)% ,
$
?/
P$DD$EF
$ compound #P% which consists of a ben9ene ring gave the following tests.
#a% gave characteristic colour with neutral
(
'eCl
#b% gave TollenIs test but not JehlingIs test
#c% showed the presence fo one methoxy group. 'ompound #P% on oxidation followed by
decarboxylation followed by reaction with 1r
&
gave 'ompound #P% gave only three mono substituted
product when electrophilic substitution reaction was done. $lso when #P% is heated with Gn dust it gives a
compound #$% which gives ( mononitro derivatives. 'ompound #P% on treatment with H1r gave
compound #M% which on reaction with sodium acetate in the presence of acetic anhydride to give
compound #=%. compound #P% on reaction with 'H
(
'H0 gave a compound #D% which on heating gave
compound #T%
"4!. The compound #$% must be
#$% #B% #'% #)%
"4". The compound #P% must be
#$% #B%
Sri Chaitanya Page 30 Vizag

#'% #)%
"4&. The compounds #=% and #D% must be
#$% and #B%
#'% #)% $ll
Passage
The proton + neutron and electron are the three subatomic particles important in an atom .The particles
occupy two regions . Protons and neutrons occupy the central place of the nucleus and electron the vast
space out side the nucleus.
,eutron transfer does not ta6es place in ordinary chemical reactions.Proton transfer
constitutes acidbase reactions .Flectron transfer constitutes redox reactions .=edox reactions are essential
for life. Photo synthesis and =espiration are two prime examples .=edox reactions also allow 6ey thermo
dynamic quantities to be measured as demonstrated in this problem .
Eiven the following information
( )
( )
!
!..884 a,
s
Ag e Ag ) V
+
+
( ) ( )
( )
!
!.."( a,
S s
AgBr e Ag Br ) V

+ +
( )
( )
!
(
&4.2! ?
a,
f G NH KJ mol
( ) ( )
( )
!
(
&
".."& ? f a, G Ag NH KJ mol
+


B r O
3
H O B r
B r
B r
( a 5 )
( a 5 )
( a 5 )
2
+ 1 . 4 9 1 V
+ 1 . 5 8 4 V
x
".//" V +
"4(. *hat is x in the above 7atimer diagram 3
#$% ".4(/< #B% ".!8:< #'% (.!.2< #)% "./"/ <
"4/. $ galvanic cell using standard hydrogen electrode as an anode is constructed in which the over all reaction
is ( ) # %
& # % & # % & # % (
& & & a, a,
l g l
Br H H O Br H O
+
+ + +
. Dilver ions are added until $g1r precipitates at the
Sri Chaitanya Page 31 Vizag

cathode and
Ag
+
1
]
reaches !.!4M.The cell voltage is measured to be "..&" < .
!
)
for the galvanic cell is
approximately
"(
/.:8 "! Ksp of AgBr


#$% "..(/ < #B% &."8 < #'% ".!42< #)% !.(&<
"42. Wsing the data given in the passage and ?or in the above two questions +which of the following can be
calculated3
# i % Dolubility of $g1r in a !." M aqueous solution of ammonia at
!
&2 C
# ii % ( ) ( )
!
f a, G Ag
+

# iii % Dolubility of bromine in the form of


&# % a,
Br
in water at
!
&2 C
# iv%
sp
K
of
# % s
AgBr
at
!
&2 C
#$% iii and iv #B% i+ii and iii #'% i + iii and iv #)% i +ii +iii and iv
Passage
$ salt #$% when heated with
& & .
K Cr O
and conc.
& /
H SO liberates a gas which is absorbed in NaOH
solution.The NaOH solution turns yellow.*hen this solution is acidified with acetic acid and lead
acetate solution is added + a yellow precipitate #1% is formed.
*hen #$% is mixed with
&
MnO and heated with conc.
& /
H SO +a gas #'% is evolved
which turns starchiodide paper blue
"44. The acidic radical present in the salt #$% is
#$%
(
NO

#B% Cl

#'%
&
S

#)%
I

"4.. The compound formed which turns NaOH solution yellow is


#$%
& & .
Na Cr O
#B%
&
Na S #'% NaI #)%
& /
Na CrO
"4:. *hat is the colour of gas which is evolved when salt#$% is heated with
&
MnO and
& /
H SO
#$% <iolet #B% 1rown #'% Ereenish yellow #)% 1lue
Passage
Hoffmann bromamide reaction involves conversion of a carboxylic acid amide into an amine with a loss of
carbon atom on treatment with aqueous sodium hypo bromite

R
C N H
2
O
R
B r
2
N a O H
&
NH
+ N a B r + N a
2
C O
3
The mechanism is+

C
N
O
H R
OH
H
&
H O
C
N
O
H
Br -Br
Br
R C
N
O
H
R
Br
OH
&
H O
6*e(1) 6*e(2)
6*e(3)
C N
O
Br R
R
-Br
6*e(7)
al82l"so'2ana*e
N C O
N C O
OH
R
N
C
OH
O R
N
H
C
O
O
HOH
6*e(5)
6*e(%)
6*e(9)
R-
&
NH +
&
CO
+OH
(
HCO

R
"48. If the amide is optically active and the stereogenic centre is directly lin6ed to carbonyl group then step #&%
occurs
#$% *ith retention of configuration #B% *ith complete inversion of configuration
#'% *ith partial inversion of configuration #)% 1y a reversible reaction
".!. *hich of the following will not give Hoffmann bromamide reaction 3
Sri Chaitanya Page 32 Vizag

#$%

(
CH
C
O
&
NH
#B%

C
O
N H
B r
#'%

C
O
N H
2
#)%

(
CH
C
O
N H
".".

C O O H
( " ) N &
3
, H e a *
( " " ) K O H , B r
2
, H e a *

( : )
( " ) N H
3
, H e a *
( " " ) K O & , B r
2
,
( ; )
- and C in the above sequence of reactions are respectively
#$%
an#
NH
2 N&
2
#B%
an#
N&
2 NH
2

#'%
an#
N&
2 N&
2
#)% ,o reaction in both the two paths
P$DD$EF
Jor the reaction + aA bB + products+rateQ [ ] [ ]
.
a b
K A B where H@I is rate constant.If the reaction involves
different reactants with the same concentration at all times +then the general form is [ ] [ ]
n !
A K A
!t

+which on integration gives
[ ]
( )
" "
!
" "
"
n n
n K t
A
A


1
]
.If the concentrations of one or more than one reactants are
in large excess than the other or one of the reactant acts as a catalyst+the concentrations of these
species remain same and can be ta6en as constant and hence reduction in order of reaction .In heterogeneous
catalysis+ it is assumed that the reaction occurs on the surface and that the adsorbed species obey the
7angmuir adsorption isotherm.The surface reaction rate is proportional to the fraction adsorbed . Jor
Pr A o!*ts +
.
"
A
A
K b p
(ate
bp

+
".&. $ gaseous substance decomposes according to the over all equation +
( & &
" (
& &
AB A B + .The variation of
the partial pressure of
(
AB
with time #starting with pure
(
AB
% is given below at
!
&!! C
(
# % : ! 2.! "2.! (2.!
# % 44! ((! "42 :&.2
-ime h
pAB mmHg
The decomposition is irreversible .The rate constant is nearly
#$%
/ "
( "! h

#B% 44 mm Hg
"
h

#'% !."(:4
"
h

#)%
/ " "
( "! h mm Hg

".(. $t
!
&2 C and at a constant pH of 2+ the inversion of sucrose proceeds with a constant half life of 2!!
min.$t the same temperature +but a pH of /+the half life would be
#$% 2!! min #B% 2! min #'% 2!!! min #)% /!!.min
"./. The platinum catalysed decomposition of HI obeys the rate law+
"
r K at high pressure with
"
2!! ? sec K mmHg at
!
"!! C . $t low pressures+ the rate law becomes
&
r K .pHI with
"
&
2!sec K

at
!
"!! C .'alculate the HI pressure at which the value of rate should be
&2! ? sec mmHg
at
!
"!! C
Sri Chaitanya Page 33 Vizag

#$% "! mm Hg #B% & mm Hg #'% 2 mm Hg #)% 2! mm Hg
P$DD$EF
0rganic compounds undergo different types of substitution reactions .$romatic systems generally undergo
electrophilic substitution reactions. ,ucleophlic substitution reactions may also occur in them if only
electron withdrawing groups are present as substituents .'ompounds li6e al6yl halides usually undergo
nucleophilic substitution reactions .These reactions are influenced by electronic factors mainly.There is
the posibility of attac6 by an electricphile occuring on the ring carbon to which the substituent is already
attached
".2. *hich of the following is correct with respect to higher yield of the product 3
#$%

(
CH COCl
(
AlCl
( ' a * a l 2 * " ' 5 ( a n * " * 2 )
C O C H
3
#B%

C M e
3
M e
3
C
C M e
3
N O
2
+

-
C M e
3
N O
2
M e
3
C
C M e
3
B F
7

#'%


N
N

N H
2
N a N O
2
H C l
N H
2
H
N
#)%

( (
# % . CH C COCl
C O . C M e
3
$ l C l
3
".4. *hich of the following is the main product of the given reaction3

C H
3
O
R - O
O
+
#$%

C H
3
#B%

C H
3
O
#'%

O
C H
3
#)%

O
C H
3
"... *hich of the following compounds favour &
N
S
reaction more readily3
#$%

!
C H
2

#B%

C H
3
C H
2
!
#'%

C H
2
!
O
2
N
#)%

C H
C H
2
!
C H
P$DD$EF
$ factory+ producing methanol+ is based on the reaction:
'0 O &H
&

'H
(
0H
Hydrogen ; carbon monoxide are obtained by the reaction
'H
/
O H
&
0

'0 O (H
&

Three units of factory namely+ the \reformer] for the H
&
and '0 production+ the \methanol reactor]
for production of methanol and a \separator] to separate 'H
(
0H from '0 and H
&
are
schematically shown in figure
'H
/

O
H
&
0
'0
O
H
&

'0
O
H
&

O
'H
(
0H

'H
(
0H

Sri Chaitanya Page 34 Vizag
=eformer Methanol
=eactor
Deparator
() () ()
()

Jour positions are indicated as + + and . The flow of methanol at position is "!
(
mol?sec. The
factory is so designed that
&
(
of the '0 is converted to 'H
(
0H. Fxcess of '0 and H
&
at position are
used to heat the first reaction. $ssume that the reformer reaction goes to completion.
$t the position #% mole ratio of '0 to H
&
is
"
(
'0 O &H
&

'H
(
0H S H
r
Q 2!! =
".:. *hat is the flow of '0 and H
&
at position #%3
#$% '0 : "2!! mol?sec S H
&
: (!!! mol?sec
#B% '0 : "2!! mol?sec S H
&
: /2!! mol?sec
#'% '0 : "!!! mol?sec S H
&
: &!!! mol?sec
#)% '0 : "2!! mol?sec S H
&
: &!!! mol?sec
".8. *hat is the flow of '0 and H
&
at position #%3
#$% '0 : 2!! mol?sec S H
&
: "!!! mol?sec
#B% '0 : 2!! mol?sec S H
&
: "2!! mol?sec
#'% '0 : 2!! mol?sec S H
&
: &!!! mol?sec
#)% '0 : 2!! mol?sec S H
&
: &2!! mol?sec
":!. $mount of energy released in methanol reactor in " minute 3
#$% "&!! 6cal #B% 4!!! 6cal #'% "&!!! 6cal #)% 4!!!! 6cal
P$DD$EF
'ovalent compounds undergo hydrolysis via D
,
"

#unimolecular nucleophilic substitution% or D
,
&
#1imolecular nucleophilic substitution% mechanism+ for D
,
& mechanism within the
molecule atom should have at least one vacant orbital+ if it is not there then hydrolysis
ta6es place via D
,
" mechanism #dissociative step% in drastic condition
":". *hat are the hydrolysis products of 1e'l
&
3
#I% U1e#0H%
/
V
&
#II% 1e#0H%
&
#III% H'l #I<% 1eH
&
#$% I+ III #B% II+ III+ I< #'% I+ II+ III #)% II+ III
":&. 7east probable product formed on hydrolysis of 1'l
(
is
#$% H'l #B% U1#0H%
/
V

#'% 1#0H%
(
#)% ,one
":(. ''l
/
is inert towards hydrolysis under ordinary conditions because
#I% ,o vacant orbital on attac6ing site of 'atom
#II% ''l
/
is non polar and does not react with polar H
&
0 molecule
#III% 1ond dissociation energy of ' 'l bond is very high
#I<%H
&
0 molecule cannot approach the antibonding M.0. of ' 'l bond due to steric crowding.
Delect correct code:
#$% I+ II and I< #B% I and I< #'% I and II #)% I+ II+ III and I<
P$DD$EF :
@etoenol interconversion is also called 6etoenol tautomeri9ation or enoli9ation. The
interconversion of the tautomers can be catalysed by either acids or bases. In a basic solution+
hydroxide ion removes proton from the carbon of the 6eto isomer+ forming an enolate ion. Protonation
on oxygen forms the enol tautomer+ whereas protonation on the carbon reforms the
tautomer.
Basecatal,&ed 0etoenol intercon'ersion$
Sri Chaitanya Page 35 Vizag

R
R
H
O
R
R
O
O H
H
R
R
OH
OH
-
+ OH
-
8e*o <or= enola*e "on
enol <or=
In an acidic solution+ the carbonyl oxygen of the 6eto tautomer is protonated and water removes a proton
from the carbon+ forming the enol.
Acidcatal,&ed 0etoenol intercon'ersion$
R
R
H
O
R
R
O
H
H
R
R
OH
8e*o <or=
enol <or=
+
H
+
H
2
O>
+
H
3
O
+
":/.
Ph
O
O&
-
?&
2
O
(rolon+e#)
(P)
Jinal product P is

#$%
CH
3
Ph
O
&
&
#B%
C&
3
Ph
O
&
&
#'%
Ph
O
#)%
C&
3
Ph
O
&
H
":2.
O
O
$bove interconversion ta6es place in
#$% $cidic medium #B% 1asic medium
#'% 1oth #)% ,eutral medium #pHQ. at &8:@%
":4. )ecreasing order of enol content of the following compounds in liquid phase

O
O
(1)
O
(2)
O
(3)
C H
3
O/*
O
(7)

#$% /B(B&B" #B% &B"B(B/ #'% "B&B(B/ #)% (B"B&B/
P$DD$EF
*hen the reactants are mixed in a chemical system+ the system will proceed spontaneously to a position
of lower free energy+ and the system will eventually achieve equilibrium. $t any point along the way from
Sri Chaitanya Page 36 Vizag

the pure reactants to equilibrium+ the reactants are not at standard states. The change in Eibbs free energy
for a reversible reaction under these non standard conditions+
r
E is related to
r
E
!
by the equation

r
E Q
r
E
!
O =T ln M
where M is the reaction quotient. Jurther more+ as long as E is negative L that is the reaction is
\descending] from the free energy of the reactants to the equilibrium position L the reaction is
spontaneous. Fventually the system reaches equilibrium because no further change in concentration of
reactants+ products is seen at this point. E must be 9eroS that is there is no further change in free energy
in system. Dubstituting E Q ! and M Q @ in the equation+
! Q E
!
O =T ln @ or E
!
Q =T ln @
":.. The standard free energy of formation of # % NaBr s % is
&/2 ? kJ mol
. 'alculate
!
G
for the reaction
&
& # % & # % # % NaBr s Na s Br l +
#$% &/2kJ #B% /8!kJ #'% 48/kJ #)% /8!kJ
"::. $t (!!@+ the standard free energy of formation of
& 2
# % N O g
is
/& ? kJ mol
. 'alculate G for the
following reaction
& & & 2
& # +: % 2 # +" % & # +: % N g bar O g bar N O g bar +
#Eiven : ln & Q !..+ = Q : >?@ mol%
#$%
8/./ ? kJ mol
#B%
2../ ? kJ mol
#'%
...4 ? kJ mol
#)%
:/ ? kJ mol
":8. *hat is partial pressure of H'l #g% above an aqueous solution that is &M in H
O
and ".2M in
&!!!
.
Cl at K

. =eaction is
# % # % # % H a, Cl a, HCl g
+
+
Eiven : = Q :.!>? mol. @ :
f
E
o
#H'l+ g% Q 82 6> ? mol+
f
E
o
#'l

+ aq% Q "(".:/:6> ? mol. $ll data


at
&!!!
.
@.
#$%
.
( "! bar

#B%
.
"! bar

#'%
4
( "! bar

#)%
:
(.(( "! bar

Passage
Preparation of Erignard reagent
= L - O Mg
&
Ft 0
= Mg -
+
#0rgano magnesium halide%
Erignard reagent may be made from primary+ secondary and tertiary al6yl halide as well as from vinyl
halide and aryl halides. Erignard reagent is strong nucleophile and strong base
"8!.
/* C H
3
O
(") PhM+Br
(P)
("") H
+
Ma5or product #P% is
#$%
OH
Me
Ph
/*
#B%
Me
Me
Ph
/*
#'%
OH Ph
Ph
Ph
#)%
OH
Me
Ph
Ph
"8". In which of the following reaction tertiary alcohol #ill not be obtained as a product
#$%
CH
3
O
(") /*M+Br
("") H
+
#B%
Cl
O (") PhM+Br (e!'ess)
("") H
+

Sri Chaitanya Page 37 Vizag

#'%
Cl
O
O
/*
(") /*M+Br(e!'ess)
("") H
+
#)%
H
O (") PhM+Br (e!'ess)
("") H
+
"8&.
MeM+Br
(P)
O
/*
OH
Ph
(")PhM+Br
("")
(@)
H
+
Fnd product #M% is
#$%
H
Ph
O
#B%
CH
3
Ph
OH
#'%
Ph
OH
Ph
#)%
Ph
O
Ph
Passage :
$+1 and ' are three complexes of chromium #III% with the empirical formula
"& 4 (
CrH O Cl
. $ll the three
complexes have water and chloride ions as ligands. 'omplex $ does not react with concentrated
& /
H SO
+
where as complexes 1 and ' loses 4..2N and &..!&N of their original weight respectively on treat with
concentrated H
&
D0
/
"8(. The complex 1 is
#$% ( )
& (
4
Cr H O Cl 1
]
#B% ( )
& & &
2
. Cr H O Cl Cl H O 1
]

#'% ( )
& & &
/
.& Cr H O Cl Cl H O 1
]
#)% ( )
& ( &
(
( Cr H O Cl H O 1
]
"8/. Delect the correct statement
#$% conductance in these complexes is in order 'A1A$
#B% F$, of chromium is not identical #'% ,uclear spin of chromium is identical
#)% ,on reactivity of $ with conc.H
&
D0
/
is due to absence of Cl outside coordination sphere
"82. The 'omplexes can show
#$% 'oordination Isomerism #B% 0ptical isomerism
#'% 7in6age isomerism #)% Hydrate isomerism
Passage :
2:. *.H ,ernst derived a mathematical relationship between the emf of a cell #F
cell
% and the concentration
of reactants and products in a redox reaction under nonstandard conditions. The nernst equation for a
redox reaction of the type
aA bB *C !/ + + is
!
ln
*ell *ell
(-
) ) +
n'

$t &8: @ .
!
!.!28"
log
*ell *ell
) ) +
n

*here M is the reaction quotient. $t equilibrium + there is a no net transfer of electron+ so F Q ! and MQ @+
where @ is the equilibrium constant. *e can also apply nernst equation for a half cell to calculate
oxidation or reduction potential
"84. *hat is the FMJ of represented cell at &8: 6. ( ) ( ) ( )
&
+ !." + !." + !." Ag Ag a, M H a, M H g bar Pt
+ +
Eiven :
!
?
!.:
Ag Ag
) V
+

#$% !...< #B% !.:&8< #'% !...< #)% ,one of these
"8.. Jind the solubility product of a saturated aqueous solution of $g
(
P0
/
at &8: 6 if the emf of the cell
( ) ( )
( /
+ !.!" !."":& &8: . Ag Ag satrrate! Ag PO Ag a, M Ag is V at k
+ +
#$%
"4
"!

#B%
"2
&.. "!

#'%
".
(.(( "!

#)%
"4
".(( "!

Sri Chaitanya Page 38 Vizag



"8:. *hat would be the reduction potential of an electrode at &8: @+ which originally contained " M @
&
'r
&
0
.

reduce all
&
& .
Cr O

to 'r
(O
. $ssume pHQ".! and which was treated with 2!N of the Dn necessary to reduce
all
&
& .
Cr O

to 'r
(O
. $ssume pH of solution remains constant.
Eiven : & (
& .
!
? +
&.(!(
".(( S log & !.(S !.!4
Cr O Cr H
(-
) V
'
+ +

#$% ".&:2 < #B% "."8( < #'% ".":. < #)% ,one of these
Passage :
$romatic compound are these that meet the following criteria
#i% The structure must be cyclic+ containing ( ) / & +
electrons
#ii% Fach atom in the ring must have unhybridi9ed p orbitals
#iii% Wnhybridi9ed porbitals must overlap orbitals
#iv% Dtructure must be planar
In antiaromatic compound ( ) /n
electron are delocali9ation+ but delocali9ation of pi electrons over the
ring increasing the electronic energy
"88. *hich of following compound is aromatic
#$% #B% #'% #)%
&!!. *hich of following is anti aromatic
#$% #B% #'% #)%
&!". In which of following reaction product formed is aromatic
#$% #B% #'% #)% $ll
P$DD$EF
$ white crystalline compound soluble in water+ has no reaction with dil. H
&
D0
/
. The salt on strong heating
gave an acid gas that is paramagnetic which on cooling transformed into diamagnetic molecule+ leaving
behind on yellow residue+ changed to white on cooling. The salt solution gave a white precipitate with
ammonia+ dissolved in excess ammonia forming a complex. The salt when heated with cobalt nitrate gave
a green coloured mass. The salt solution gave a bluish white precipitate with potassium ferrocyanide
solution
&!&. The acid gas liberated is
#$%
&
CO
#B%
&
NO
#'%
&
SO
#)%
& (
P O
&!(. Jrom the data most probable salt
#$%
(
MnSO
#B%
( &
# % Pb NO
#'%
(
NiCO
#)%
( &
# % &n NO
&!/. The colourless complex formed is
#$%
( )
&
(
/
Pb NH
+
1
]
#B%
( )
&
(
4
Mn NH
+
1
]
#'%
( )
&
(
/
&n NH
+
1
]
#)%
( )
&
(
/
Ni NH
+
1
]
Passage :
$rndt L eistert reaction consists in increasing the length of the carbon chain by one methylene group in
carboxylic acid.
&
( COOH ( CH COOH . However carboxylic acid should be converted first to an
acid chloride. The sequence of steps may be shown as
Sri Chaitanya Page 39 Vizag

& & & &
(
&
&
& &
N
SOCl CH N Ag O H OH
CH Cl A
A B /
C )
( COOH ( CO Cl (COCHN ( CH C O ( CH COOH


&!2. The product obtained on treatment of H'I with $g
&
0 and
K
&
( NH will be
#$%
K
( COO(
#B%
K
( CONH(
#'%
K
&
( CH CO NH( #)%
& &
( CH CONH
&!4. If
"/
& &
CH N is used propanoic acid gives
#$%
"/
( & &
CH CH CH COOH #B%
"/
( & &
CH CH CH COOH
#'%
"/
( & &
CH CH CH COOH #)%
"/
( & &
CH CH CH COOH
&!.. The application of this reaction of Malonic acid gives
#$% oxalic acid #B% succinic acid #'% glutaric acid #)% adipic acid
Passage :
The electromotive force #emf% is the maximum voltage of a voltaic cell. It can be directly related to
maximum wor6 that can be done by the cell. The standard free change+ standard emf and equilibrium
constant are all related. $n electrode potential depends on concentration of the electrode substance but not
on the stoichiometry of the electrode reaction. $ccording to ,ernst equation
!
!.!28
log ) ) +
n
at &2
!
' emf of the cell is 9ero at equilibrium. Jree energy is related to the electrode
potential as G n')
&!:. Eiven
( )
(
(
a, s
'e e 'e
+
+
F
!
Q !./2<
( )
&
&
a, s
'e 'e e
+
+
F
!
Q !.!/<
*hat is the standard electrode potential of
( ) ( )
( &
a, a,
'e e 'e
+ +
+
#$% !./"< #B% ".&.< #'% !./8< #)% ".&.<
&!8. ( )
( )
a,
s
C e C
+
+
F
!
Q !.2&<
( ) ( )
&
a, a,
C e C
+ +
+ F
!
Q O!."4<
!
G
in @>?mol for the disproportion of 'u
O
is
#$% (././ #B% 48./: #'% (/../ #)% O(././
&"!. Jor the reactions
&
/ &
: 2 / MnO H e Mn H O
+ +
+ + + F
!
Q ".2"<
&
& &
/ & & MnO H e Mn H O
+ +
+ + + F
!
Q ".&(<
Then for the reaction
/ & &
/ ( & MnO H e MnO H O
+
+ + +
The equilibrium constant is U $nti log !.&."Q".:44V
#$% ".:44 x "!
:4
#B% " #'% ".:44 x "!
:2
#)% ".:44 x "!
:4
Passage :
0n dissolving !.!&4/ g of a compound #$% in (.! g of camphor+ the melting point of camphor is lowered
by /
!
'. and undergoes acetylation on treatment with acetyl chloride. 0n reacting #$% with H'l and Gn'l
&

a dense oily layer is quic6ly formed. $lso on passing over alumina at (2!
!
'+ #$% yields a compound #1%
which on o9onolysis gives #'% and #)% give a yellow precipitate with &+/ L dinitrophenylhydra9ine but
only #'% reduces JehlingIs solution. #'% also forms a resinous substance with concentrated ,a0H
#@
f
for camphor Q /! @ 6g mol
"
%
&"". The molecular formula of H$I is
#$%
/ "!
C H O
#B%
4 "/
C H O
#'%
2 "&
C H O
#)%
. "4
C H O
&"&. '+ ) respectively are
Sri Chaitanya Page 40 Vizag

#$%
( ( (
+ CH CHO CH CO CH
#B%
( & ( (
CH CH CHO CH CO CH

#'%
( & & ( (
CH CH CH CHO CH COCH
#)%
& ( (
+ CH O CH COCH
&"(.
NaOH
C / + the product #s% may be
#$%

hydroxy aldehyde #only% #B%

hydroxy 6etone #only%


#'%

hydroxy aldehyde O

hydroxy 6etone
#)% formate ion O &
!
alcohol
Passage :
In an elementary act of a chemical reaction does not occur each time reacting molecules collide only those
molecules react that have sufficient energy to brea6 the bonds in the initial particles and thus create the
possibility of formation of products. 'onsequently every reaction is characteri9ed by a definite energy
barrier. This is 6nown as threshold energy. To surmount it+ certain excess energy #in comparison with the
average energy of the molecules at a given temperature% is needed 6nown as activation energy to result in
formation of products. The dependence of rate constant H@I of a reaction on activation energy HF
a
I is
expressed by $rrehenius equation
?
.
a
) (-
K Ae

where $ is frequency factor+ T is absolute temperature and = is gas constant. Dubstance $ is


transformed into substance ' according to the reaction
( "
&
K K
K
A B C
+ The energy diagram of the process is given as
&"/. *hich of the following is correct
#$%
" & & (
K K an!K K > >
#B%
" & & (
K K an!K K < >

#'%
" & & (
K K an!K K > <
#)%
" & & (
K K an!K K < <
&"2. In the above diagram+ activation energy of B A is (! 6>?mole and the average energy difference
1etween $ and 1 is &! 6>?mole. The equilibrium constant at &.
o
C is #assume Jrequency factor is
'onstant%
#$%
(
(.!& "!

#B% &.:& x "!


2
#'%
/
(.(" "!

#)%
(
/."& "!

&"4. In the same transformation if @


"
B@
&
and @
&
B@
(
which of the following statement is correct
#$% The threshold energy of A B and B C are same and &
nd
step is endothermic
#B% The threshold energy of A B and B C are same and &
nd
step is exothermic
#'% The threshold energy of A B and B C are different and &
nd
step is exothermic
#)% The threshold energy of A B and B C are different and &
nd
step is endothermic
Passage
x and y are two isomers having molecular formula #'
4
H
"&
0%
Sri Chaitanya Page 41 Vizag

&".. If HCI is tertiary alcohol with five carbon ring. Then it on treating with above series of the
reagents then the product obtained is
#$% #B% #'% #)%
&":. *hat is the structure of #x%
#$% #B% #'% #)%
&"8.
* is
#$% #B% #'% #)%
Passage
=eal gases deviate from ideal behaviour and the extent of deviation is expressed in terms of
compressibility factor #G% which is the ratio of the observed molar volume to the ideal molar volume. G is
a function of pressure ; temperature for real gases. If GQ"+ then it is an ideal gas and if GB"+ then the
gases are less compressible and for easily liquefiable gases+ GA"
&&!. *hich of the following statements is correct
#$% the compressibility factor for ideal gases depends on temperature and pressure
#B%
-
!&
!P
_

,
for real gases is independent of pressure
#'%
-
!&
!P
_

,
for all real gases have same value #)%
-
!&
!P
_

,
for different real gases have different values
Sri Chaitanya Page 42 Vizag

&&". *hich of the following statement is correct for gas $ having molar mass "4g and density !..2g?7 at & atm
and &.
!
' temperature
#$% Jorce of attraction are dominating than force of repulsion among the gas molecules
#B% Jorce of repulsion are dominating than force of attraction among the gas molecules
#'% Jorce of attraction equals to force of repulsion
#)% ,one
&&&. The graphs between compressibility factor and pressure can be explained by <an der *aalIs equation
&
U VU V
m
m
a
P V b (-
V
+
. The value of GA " by
#$% ignoring the constant a #B% ignoring the constant b
#'% ignoring both a ; b #)% retaining both a ; b
Passage
&&(. Type of hybridi9ation in compound #@%
#$%
& (
! sp #B%
( &
sp ! #'%
&
!sp #)%
(
sp
&&/. *hich of the following set of reagent is suitable to get #J% from #E%
#$% H
&
0
&
in neutral #B% H
&
0
&
in basic medium
#'% H
&
0
&
in acidic medium #)% none
&&2. *hich of the following gas is turning the filter paper dipped into ( )
/ & &
MnSO H O +
solution brownish
blac6
#$% gas ) #B% gas > #'% gas ' #)% none
Passage
)uring the distillation of binary liquid solution the following points are helpful
". $ liquid boils at a temperature at which its vapour pressure becomes equal to surrounding atmospheric
pressure.
&. $ liquid boils at a constant temperature when the composition of the liquid and of vapour are same and
vice versa
(. 0n progressively raising the temperature of liquids+ liquid with high vapour pressure reach its boiling
point earlier
/. The residue left behind after a part of liquid is removed as vapour has a boiling point which is either
equal to or more than boiling point of initial liquid
2. The component whose further addition increases the vapour pressure is 6nown as vapour pressure
increasing component #<PI%
Jractional distillation of ideal and nonideal binary liquid solution of liquids $ and 1 are given below
Sri Chaitanya Page 43 Vizag

&&4. $ccording to the figure I+ when first condensate is removed+ the composition of $ is
#$% =ich in condensate than original liquid #B% Poor in condensate than original liquid
#'% )oes not change #)% ,one
&&.. Jrom the figure II+ which is correct statement
#$% In the region of curves from 1 to '+ $ is the <PI 'omponent
#B% In the region of curves from 1 to '+ 1 is the <PI component
#'% In the region of curves from $ to '+ 1 is <PI component
#)% In the region of curves from $ to '+ both $;1 are <PI components
&&:. Jrom figure I the boiling point of first condensate '
"
+ Jirst liquid residue#7
"
% and second condensate #'
&
%
are in the order
#$%
" & "
C C # > >
#B% " " &
# C C > >
#'% " & "
# C C > >
#)% & " "
C # C > >
Passage
)ifferent special arrangements of atoms that result from restricted rotation about a single bond are called
conformation. Dtability of conformer depends on torsional strain+ steric strain+ dipoledipole attraction and
intramolecular hydrogen bonding
&&8. *hich one of the following statements is not correct3
#$% Eauche form of nbutane is less stable than anti form due to gauche interaction
#B% nbutane has four different conformers
#'% Eauche form of nbutane is less stable than the eclipsed form
#)% Fnergy barrier between anti and fully eclipsed form is /2 6cal?mole
&(!. *hich one of the following conformers of (amino&butanol is most stable3
#$% #B%
Sri Chaitanya Page 44 Vizag

#'% #)%
&(". $rrange stability of different conformers of cyclohexane in decreasing order
"% 'hair &% Half chair (% 1oat /% Twist boat
#$% "+ /+ (+ & #B% "+ (+ /+ & #'% "+ &+ (+ / #)% "+ /+ &+ (
Passage
$ certain metal #$% is boiled in dilute nitric acid to give a salt #1% and an oxide of nydrogen #'%$n
aqueous solution of #1% with brine solution gives a precipitate #)% which is soluble in ammonium
hydroxide . 0n adding aqueous solution of #1% to hypo solution+ a white precipitate #F% is obtained . #F%
on standing turns to a blac6 compound #J%. Metal $ is also present in pyrargyrite
&(&. *hen precipitate #)%is dissolved in excess of
/
NH OH
+ a soluble complex is obtained . The hybridi9ation
of metal in that complex is
#$%
sp
#B%
&
sp
#'%
&
!sp
#)%
& (
! sp
&((. The formula of blac6 precipitate #J% is
#$%
& & (
Ag S O
#B%
&
Ag O
#'%
&
Ag S
#)%
HgS
&(/. *hen ppt ) is reacted with
& /
K CrO
. It gives a coloured ppt which is
#$%
& /
Ag CrO
+ orange red #B%
/
AgCrO
S bric6 red
#'%
/ & ( /
U # % # % V K Ag CrO NH
S bric6 red #)%
/ /
# % Ag NH CrO
Sdar6 red
Passage
<1T describes the bonding in terms of hybridi9ed orbitals of the central atom or ion. The theory mainly
deals with the geometry #i.e.+ shape% and magnetic properties of the complex.The salient features of the
theory are
#"% The central metal loses requisite number of electrons to form the ion. The number of electrons lost is
the valency of the resulting cation. In sum cases+ the metal atom does not lose electrons.
#&% The central metal ion or atom ma6es available a number of empty s+ p and d atomic orbitals equal to its
coordination number. These vacant orbitals hybridi9ed together to form hybrid orbitals which are same in
the number as the atomic orbitals which are same in the number as the atomic orbitals hybridi9ing
together. They are equivalent in energy and have definite geometry
&(2.
&
( /
U # % V C NH
+
has ^^^^^^^^^^^ hybridi9ation
#$%
(
sp
#B%
&
!sp
#'%
&
sp !
#)% ,one of these
&(4. *hich complex has 9ero magnetic moment #spin only%
#$%
&
/
U V NiCl

#B%
&
/
U # % V Ni CN

#'%
(
4
U # % V Cr CN
+
#)% $ll of these
&(.. *hich of the following cyano complex would exhibit the lowest value of paramagnetic behavior 3
#$%
(
4
U # % V Cr CN

#B%
(
4
U # % V Co CN

#'%
(
4
U # % V 'e CN

#)%
(
4
U # % V Mn CN

Passage
Phenol undergoes reactions+ which are normally not shown by alcohols.e.g.+ when PhOH is treated with
&n + it is converted into ben9ene. Jormylation of phenols with chloroform in al6aline solution is 6nown as
=eimer Tiemann reaction. In this reaction+ it is believed that
(
CHCl
and NaOH react to from carbene
which reacts with phenol in its 6etonic form to give product
Sri Chaitanya Page 45 Vizag

&(:.
OH
CHO
S
&n Hg
HCl
A

$ is
#$%
(
CH
#B%
(
CH
OH
#'% 1oth #$% and #1% #)%
O
C
O
&(8.
HO
HO
%
(
& &
%
i CHCl NaOH
CH I NaOH
ii H
0 1
+
+
+

In the above reaction + - is
#$%
HO
HO
CHO
#B%
HO
HO
CHO
#'% #1% is ma5or + #$% is minor #)% ,one of these
&/!. In the above reaction+ C is
#$%
HO
HO
& &
CH CH OH
#B%
HO
HO
& (
CH OCH

#'%
CHO
O
O
&
H C
#)%
CHO
(
CH O
(
CH O
Passage :
$ complex compound of chromium contains five
(
NH
molecules+ one nitro group and two chloride ions
for one
(
Cr
+
cation. 0ne molecule of this compound produces three ions in aq.solution+ on reacting with
excess of
(
AgNO
solution+ two moles of AgCl get precipitated.
&/". The formula of the complex compound is
#$%
& ( / (
U # %# % V CrCl NO NH NH Cl
#B%
( 2 &
U # % V . CrCl NH Cl NO

#'%
& ( 2 &
U # %# % V Cr NO NH Cl
#)%
( 2 & &
U # % V . Cr NH NO Cl
&/&. The types of isomerism shown by the complex compound is
#$% Eeometrical+ ioni9ation #B% Ioni9ation + lin6age
#'% 7in6age + optical #)% Eeometrical + optical
P$DD$EF :
$n optically active compound #$%
: "&
C H
gives an optically inactive compound #1%
: ":
C H
on
hydrogenation. #$% gives no precipitate with
( &
# % Ag NH
+
and gives optically inactive #'%
: "/
C H
with
&
H in
presence of ,ic6el 1oride
Sri Chaitanya Page 46 Vizag

&/(. 'ompound #1% is
#$%
( & & & & (
(
T
CH CH CH CH CH CH CH
CH

#B%
( & 4 (
# % CH CH CH

#'%
( & & & & (
(
T
CH CH CH CH CH CH CH
CH

#)%
( & & & 2
( (
T T
CH CH CH CH C H
CH CH

&//. 'ompound #$% is
#$%
( (
(
T
CH CH CH CH C C CH
CH

#B%
( & (
(
T
CH C CH CH C C CH
CH


#'%
( & & (
CH CH CH CH CH C C CH
#)%
(
( (
T T
CH C CH CH C CH
CH CH

&/2. 'ompound #'% is
#$%
( & (
(
T
CH C CH CH CH CH CH
CH

#B%
( (
(
T
CH CH CH CH CH CH CH
CH


#'%
( & & (
CH CH CH CH CH CH CH CH

#)%
( &
( (
T T
CH C CH CH CH CH
CH CH

P$DD$EF
$ yellow coloured powder #$% reacts with acetic acid to form a white crystalline solid #1% which is used
for curing s6in diseases. 'omp #1% on heating gives solid #$%+ a gas #'% and a compound #)%. comp.#)% on
reacting with
&
I and
& (
Na CO
forms a yellow precipitate of compound #F%. comp. #1% when treated with a
solution of sodium carbonate gives a white ppt. of #J% and when
&
H S is passed into solution of #1%+ it
forms a blac6 ppt+ of #E%
&/4. Identify #)%
#$%
( & (
CH CH COCH
#B%
(
CH COOH
#'%
( (
CH COCH
#)% PbO
&/.. 'ompound #$% is
#$% PbO #B%
/
PbCrO #'% MnS #)%
& /
Na CrO
&/:. The white ppt. #J% is
#$%
/
NH Cl #B% &nS #'%
& 4
U # % V Ca 'e CN
#)%
( &
& . # % PbCO Pb OH
&/8.
#$% #1% #'% #)%
&2!.
#$% #1% #'% #)%
&2".
#$% #1% #'% #)%
&2&.
#$% #1% #'% #)%
&2(.
#$% #1% #'% #)%
&2/.
#$% #1% #'% #)%
&22.
Sri Chaitanya Page 47 Vizag

#$% #1% #'% #)%
&24.
#$% #1% #'% #)%
&2..
#$% #1% #'% #)%
&2:.
#$% #1% #'% #)%
&28.
#$% #1% #'% #)%
&4!.
#$% #1% #'% #)%
&4".
#$% #1% #'% #)%
&4&.
#$% #1% #'% #)%
&4(.
#$% #1% #'% #)%
&4/.
#$% #1% #'% #)%
&42.
#$% #1% #'% #)%
&44.
#$% #1% #'% #)%
&4..
#$% #1% #'% #)%
&4:.
#$% #1% #'% #)%
&48.
#$% #1% #'% #)%
&.!.
#$% #1% #'% #)%
&.".
#$% #1% #'% #)%
Sri Chaitanya Page 48 Vizag

Sri Chaitanya Page 49 Vizag