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GE,T IIT JEE >ilI (A+B)

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QUESTIONBANK ON

AC'D'TV BAS|C|TY AND TAUTOENEffiISM

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BANSAL CLA$SES
(Raj.)|NDIA. Kota-324005 "GAURAV TOWER" 10, RoadNo.-1, P. Al. 1.A., 2123244 ax'. F 24367 9 7 Tel:(0744)24237 24237 2421 38, 097,2424097, 39, (Raj.) Ajmer Tt:|..0145-2633456 92-LlC Colony, Vaishali Nagar, Bypaci,Jaipur Tel.:0141-2721107,2545066 CLASSES, Pooja Tower, Gopalpura, Gopalpura BANSAL 3 Email:admin@bansaliitiee.com Website:wo'.:r.bansaliitiee.com the The small moon can eclipse great sun, Wetoo can do great',i:ittgsif we set ourselfsin the at the rislrt lintt,

' tt' Q.l Anange the givenphenolsintheir decreasing orderofacidity:"' (I) C6H5-OH

rur@oH

(rv)o,N@oH Grr)cr-O'-oH
(D )IV > I> III> II ss ' -

Selectthe correctanswerfrom the given code: (C )rV > III> II> I ( A ) t v > I I I> I> II (B )rV> II> IU > I

Q.2 Whichoneofthefollowineisthbmostacidic?

(qo

'li,lts

(D)CH2:CH-CH3

acidity? will Q.3 Whichoneofthe followingphenols showhighest

Noz Q.4 in orderof acidit5t? Arrange following compounds decreasing the

,t"-,rC;

Noz

t/-\l
(I) C6H5-OH

GD YJ-OH cl

,r)9
OH

givenbelow: the Select correct answer fromthecodes (C)II>III>I>IV (A)III>II>IV>I (B)III>lI>I>IV Q.5 Whichone ofthefollowingis stongestacid? (B) CFCIL{OOH (A) CI-CH2-CH2-COOH

(c) cl{H2-cH2-cHrcooH
Q.6 The correctorder of acidity ofthe given acids:

(D)cH: - cooH

(I) CH3COOH willbe: (A) II > rV > IrI > I Q.7

(ID HOOC-cooH (B) I > II > III > rV

/..COOH (III) CH2\ cOOn (C) II > III > iV > I

(rv)Hooc{cH2)4{ooH
(D)II>I>IV>III

acid? Whichofthe following is weakest

(A)

Q. Bank onAcidity, Busicity & Tcutomerism

t2l

Q.8

Considerthefollowingbases: (t) o-nitoaniline @ m-nitnoaniline Thedecreasing orderof basicityis: (A)II>III>I (B)II>I>III

(IIII p-nitoaniline (C)I>II>III (D)I>III>II

Q.9

: ofthe followingaromatic amines Consider basicity the (Itr)pmethoryaniline (V)pmethylaniline (t)aniline @pnitoaniline basicityis: Theconectorderofdecreasing (D)IV>III>II>I (A)III>IV>I>II (B)III>IV>II>I (C)I>II>III>IV basic character? in Whichoneofthefollowingis least

Q.l0

( ) (A)
'I'
H-HH

(B) r(\r,\r-H

(c)-I

a)J lr

(D) -T-

tJ

Q.I I

is: having mostacidicalpha-hydrogen the Amongthefollowingthecompounds (B) CH3COCH3 (A) CH3CHO (C) cH3 -C-CH2CHO

-tl

(D) CH3-CO-CH2{O2CH3

o
(4)Benzoic acid (D) 4>3> l>2

pH order: in Q.12 Arrange ofthe givencompounds decreasing (3)Formicacid (l)Phenol (2)Ethylalcohol (C)3> 2> 4> I (A) 1 > 2>3> 4 (B)2> t> 4>3 Q.l3

order: in Anange acidity givencompounds decreasing of (ID CH3-NH{HrCH2{H2-OH (I) CH3-NH-CH2{H'{H o ([r) (cH3)3N-cHr-cH2 -oH (A)III>I>II (B)m>II>I (C)I>II>III (D)II>I>III

in solution? Giveanexplanation whichismorebasic aqueous ofthefollowingpairofcompounds, Q. I 4 In each foryornchoicer (a) (c) (e) (b) or CH3NH2 CFTNH, (d) n-PrNH, or CHrCN m-nitoanilineorpnitoaniline orHrN'/ -f \NU, CH3CONH2 C6H;l.l(CH3)2or2,6-dime*ihyl-N-N-dimethylaniline

: the Q,I 5 Fromthefollowingpair,select stongerbase (b) pmethoxyanilineorpcyanoaniline (a) (c) CH3CNor CHTCHTNH,

pyridineorpyrrole

yourreasoning each in instance. acid? Explain to Q.I 6 Whichwouldyouexpect bethestronger (b) or (a) or CCI3CO2H CHCITCOTH CH2CICO2H CHCITCOTH (c) or CH2FCO2H CHTFCH2CO2H CH,C= CH--->A+ B Q.l7 CHTCHTMgBT+

Q. Bank onAcitlity, Basicity & Tautomerism

tsI

the that ofcompunds is likelyto bethestongerbase. ofeachofthefollowingpairs Q.18 Choose member (c) OH-or SH(a) NHi orNH, (b) OH-orHrO 9-O (d) CH3CH2O- -\O I or I ll (e) CH2-C-OH

v/

or CHTCIITO- (f)M:

or NHP

the that of Q. I 9 Choose member eachof thefollowingpairsof compwrds is likely to betheweakerbase. (a) HrO or HrOo (c) Cl-, SHO) HzS,HS-, 52(d) F-, OH-, NH2-, CHt (e) HB H2O,NH3 (D OH-, SH-, SeH-

(CH.Li) is oftenused abase organic reactiorx. in as Q.20 Methyllithium (a) Predicttheproducr ofthe following acid- base reaction. cH3cH2-oH'+ cH' -Li-+ (b) Whatistheconjugate ashongbaseoraweakbase acidofCHrLi?WouldyouexpectCHrLitobe ? Q.2l (a) G) Arrange followingcompounds orderofincreasing the basicity. in CH3NH9, CH3NHCH3NH2' = CH3CH CH-, CH3CH2CHt,CHrC=C(b) CH3O-' CH3NH-' CH3cHt

offollowing aminoacids: to Q.22 Saywhichpkobelong whichfinctional groupin case z: --COOH 1.8,8.3 lo.8 cysteineHS; & G) lNH2

1iglutamicacid

: Hozc'--z\,-cooH'

I NHz

2.1g,4.25,g.67

the to of according increasingpKn( : - log Ka) Q.23 Record followingsets compounds

OH OH

(a) (b) (c) (d) (e)

-\.,\ l,l Q l,cyclohexanecarboxylicacid. | \-,\-,l-butyne,l-butene,butane acid Propanoic acid,3-bromopropanoicacid,2-nitopropanoic Phenol,o-nitophenol, o-cresol Hexylamine,aniline,methylamine

the Q.24 Explainwhichcompoundis weakerbase.

{Hz }Hz

(a )

f O l "' IO ] \.,,\.,NO.

-t^\

(b )

cH2:cH- cH:cH- cH2- or cHr :cH- cH2-

oo

oo

OH

OH

(c)

"

(d) or -J-J-.H Ho-J-J-on

6*,

- O"o
t4l

Q. Btnk onAc:idity, Btrsicity & Tuutomerisrtt

Q.25

Rankthefollowing aminesin increasing basicnature.

NH' NH, t-

(a) 19
(D

\r'
(iii)
NH'

fft1-No,

(b)

NHr l-

1.A

@*,
(i)
NH. t'

\7
CH:

(c) o
(i) (b)

o
(ii)
CH2: CH-

(ii)

(iiD

the Q.26 Arrange basicstengthofthe followingcompounds. (a) OHCH?COOCl(') (ii) GD CH = CCH3CH2-

(c)

(iii) CHz: CHC}LNH2 CH3CH2CI{2NI{2 CH= C - CIL}CL

(r)

(iD

OD
l{H-c6H5

t9
(i)
NHr t-

(ii)

o
NH" t-

(iiD
NHr t-

-,^(e) (nI"'

vl",
(iD
RCOOOH-

.A

Tr,

r'A Y
cl

(i) (D CI-

(iii)

G)

(ii)

GD

RO(iv)

NHz(v)

the order ofpko: Q.27 Set followingin increasing (i) CH3NH2 (CH3)2NH (CH)3 N, NH3 [In aqeous medium] , ,

N\.rNH

'

^,s"
tsl

Q. Bank onAcidity, Basicity & Tuatomerism

followinginincreasing orderofp\ : Q.28 Setthe Methane sulfonicacid aceticacid& methanol. 0 (D CH3-CH2- CH3,CHr: CH- CH3,CH: -CHO, CHO- CHr- CHO, CH4 Qn) (NOz)z-CHr, (NO2)3 CH CH3NO2,

(v)

CH3COOH,NOz-CHr-COOH,CH3-C-CH2-C-OH

llll oo

(vi, R Q -*$
( vrD CHO- CHr-CHO, CH3-C-CH2-C-CH3, EI-O-C-CH2-C-O-EI,

ltillltl oooo
Et-O-C-CH2 -C-CH3

il oo

tl

astongeracid. Q.29 Explainwhichis

(b) CHr-C-CH, & CH3-C-CUTCN

oo il

tl

O=C-CH:

*[.9 n,lg,J
(a)
(b)

IH .'^\

?H -^\

to Q.30 Whichof thefollowingwouldyoupredict bethestongeracid?

ox*4[_ fiycooH o, \l "o/ \J

o"

CH3- CfL - Cl12- OH or CH3- CH = CH - OH

u
rFl

Q. Bank onAcidity, Basicity & Tautomerism

16l

(c)

CH3- CH: CH- CH2- OH or CH3- CH: CH- OH (b) ethylamine orethoxideion
(d) cyclohexylamineor aniline

& base? WhY. - Q 31 Whichis a stronger (a)ethylamine oraniline

(c) phenoxideion or ethoxideion Q.32

In eachofthe following pairs which is more stable :

Ol o\N/ +
^(\

n Ol

^'(tr) "o\*/_.

o .E @)at{,,)*, - (r)

./oH ^ cHr-\us GD

o .8. t.) ."/)" , G)

Q 33

./oH t-o, -- cHz= (rr)

ln eachofthe following pairs which is more stable:

(u) cn{

fl 'c'
i{
oP H.

g
zc\ ,/\ tH, c'f

{" g
Y
t
!

^rH

.2"\ tcH, ^--

(b)\2 (D
o

\,2 . 0r)
OH

I
(c) cH,
,/\^

cs.
^ cH3 = ^--/-\-

^'b
./

/'"'-r

fi
6

CHz

0) o

Gr)

ill (d)_E- + (r)

,/"t

/\

(ID

OH

1.y.r/tt""/tt'tg'/"' (r)

a,r(

ix
,r/"t OD

/H

O:C

stable : ofthefollowingpairswhichis less Q.34 In each

r'\
,.,Qn/o \-'/ d
(r)

$r/o
o-t GD

tll

Ptr .ph \/\ 'cH'

rtl

Pb 'r/rn

(c)

\ (D

*ao,
GD

(d)cH2=cH-NH2 cH:lr.rr"="" *

of enolcontent : Q.35 In each thefollowingpairswhichwill havehigher I ,..COOEI ru' C (a) "'?. and ,/\ cHr cHr -cooEt

/.cooEt
(b) "1 -cooEt

and

.cc

I
,/\ cHz
il

I
ocH3
tl

,/\ cH:

o oo o il (c) ,zc\
cH: cHz

il

,zc\
il

cH:

and

cHs

,zc\
il

cHz

,zc\
ll

ocH3

CC C C (d) ,/\ ,/\ cH: cHz Q.3 6

oooo ll

and ,/\ cH: Ph

,/\ cHz

Ph

In eachof the following pairs which will have lessenol content :

/\8 (a)l I
\,,/

-o

Jt and ,/\
CH;

Ch,

.,ef""oU

G)V
I CI

y''Yo

a\Yo *o(_,
and CH1-CHO

(e) CH, -CHO

of Q.37 In each thefollowingpairswhichwill havelessenolcontent:

\,'o"t'

\,'ot"'

(a) O
CH3O_.2/-*.".NH

and
_N=NH

Q.38 (a)

HO'\-,/

l.

ll

and

tu)cH'1 I '

p=rz-=,.\fH-CH

= CH2

.,/

ll

Shows tautomeric formsof (a)& O).

Q. Bank onAcidity, Basicity & thutomerism

l8l

ofthe two ketones Why aretheysodifferent? ofenol in a sample belowareshown. Q.39 Theproportion o o Et ,\-co, (a)l (b)l 62%oenol | . ,\-, 14x10{Voenol \-/ suchas(A) areusuallymostlyenolized. Why is this ? Drawtheenols compounds Q.40 1,3 - dicarbonyl onthedifferentpattemofenolization. to available compoundsA&B comrnent

(A) of write thedecreasing orderof o/o enolcontent. ofthefollowingsets compounds Q.41 ln each

v\/

o (Iu)

a\lll rrr
oo (rrr)

."\
V
(rv)

o
(c)

-\ 0rr) o
,\

<\f (n.,
0v) f-\

(d)-YH
o

ilr l
(r) o
,\" GI)

o .,/\'.'

llllrl \-'2
0rr)

-YA H
o

Gv)

Ao,
(e)

(r)

(ID

Gv)

Give and which is morestable? Q.42 Out ofenol form of cyclobutanone enolforrn oftriketocyclobutane, also. reason

rn
\g

Q. Bank onAcidity, Basicity & Toutomerism

teI

o tl
L

Q.43

CH:

(r)

CHI

/''\ cDr CDr (ID

ooo llllll
,/\ cHr

C '' ,/\' 'cHr cHz OII)

Amongthese giveease enolization. of o% content enol ofacetylacetone following solvents foundas: Q.44 in is o% content Sofuent enol HrO l5 Liquidstate 76 hexane 92 gasphase 92 Explaintheobservation.
oo oNa

Q.4s

>\-.

(Major)

OH
,,\,,-

(Major) Explaintheobservation.

Q.Bank onAcidity,Basicity& Tautomerism

AOI

ANSWERKEY
Q.l Q.8 c A Q.2 Q.e B A Q.3 C

Q.4 D

Q.s

Q.6

Q.7

Q.l0 A

Q.14 (a)i,(b)ii,(c)i, (d)ii,(e)i Q.l6 (a)2; (b) l; (c) 1 Q.l8 (a)l; (b) l; (c) l; (d) l; (e)2;(Dl Q.21 (a)2<l<3;(b) l<2<3;(c) 3<l<2

Q.ll c Q . l2 B Q.l5 (a)i,(b)i,(c)ii

Q.l7

Q.l3 A

+ CH3CH3 CH3C= CMgBr

Q.l9 (a)2; (b) l; (c) l; (d) l; (e) 1; (D 3

HO2C--V,'^a-.-COOH

e.22 (D

cysteine, H:aYt?8" NH2

1 0 .8

liiy

glutarnic : 4'25 acid

z'te

*lr"
9.67

(d)2<l<3'(e)2<3<l (c)3<2<l; (b) Q.23 (a)3<2<l; 1<2<3; Q.24 (a)2; (b) r; (c) 2; (d) 2 (c) Q.25 (a)3<2<l<4; l<2<3<4; 3<l<2 ft) ; Q.26 (a) l>2>3; (b) I <2<3 (c) 3<l 4; (d) 2<l <3' (e) l<2<3; (D l<2<3<4<5 (ii) I Q.27 (i)4>3>1>2; 1<2;(iii) <2 Q.28 (i) l<2<3; (ii) l>5>2>3>4; (iii) l>2>3; (iv) l>3>4>2; (v) l>3>2; (vi) 2>l>3; (vii)3>4>2>l Q.2e (a)2; (b)2; (c) r; (d) l; (e) I Q.3I (a) I ; (b)2; (c) 2; (d) | Q.30 (a)2; (b)2; (c)2" Q.32 (a)2; (b) 2; (c) r; (d) I ; (e) I Q.34 (a)2; (b) 1; (c) l; (d) I Q.36 (a)2; O) r;(c\2;(d) l; (e)2

l; Q.33 (a)2;@\2;(c) (d)2;(e)r Q.3s (a)l;(b)2;(c)r;(d)2 Q.37 (a)2;(b)2

Q.42 enolformoftiketocyclobutane

Q.43 3>l>2

u
.il|

Q. Bank onAcidity, Basicitl; & Thutomerisnt

F4