"manishkumarphysics.

in"
1
CHEMISTRY
rnaifa+ sii, nt4+iit4 ui4 aii fif+4i r4at
(Electronic effects, acid-base strength andreactionintermediates)
1. rnaifa+ sii (Electronic effects):
t ii i :n + i-i + l-i = --- ti -i t :n + il-+ ii +tn-i t
nt+i :
1.1 sfi+ sii (Inductive effect) :
1.1.1 (+ =ini- CC-i n -l-i- <i -i nii ~i +i l - +i-i +i ni- =ni- ti - + +n-. -i +i l-i ~i i
(non polar) ti -i t l< tn (+ +i - ini 1-+ni i - +i ~- + -i tn < i- t l+ Cl =n t +i li -+i-i
+i ni- +i - nii +i ~ -ii ~li+ ti - + +ii CCl -i + i n +i ~i lzi+ = Cl =n t +i ~i l-ii- ti
i-i t . l=+ +n- Cl nii ~i lzi+ +ii zi (o-) -ii C
1
nii ~i lzi+ i-i zi (o+) --- ti i-i t
~ C
1
nii i l+ i-i lzi- i :n + i- - - t . ~- t C
1
C
2
-i + :n + i- n +i ~-i ~i ~i+li - +-i
t . l=+ +n- t i n ii l-iil- ti i-i t -ii C
2
nii t-+i =i i-i zi oo+ --- ti i-i t
:=i +i C
3
nii ii - +- l+i ,ii ~-- t-+i i-izi ooo+ --- ti i-i t. ~ii- =- i ini n
(+ lzi i +i + l- ~i zi +i = -i ti - nn-i t ~- t ii li+ ii +tni-i t
li+ ii +i l--- l-zi ,ii <lzi - l+i i =+-i t
- +- l-zi n -i +i l--t Cl =n t +i e

~i+ii + l- +i <lzi - +-i t

~- li+ ii +i l--- +i = liili- + =+- t "o -i n :n + i -i +i l,i + +ii -iii = l-ii-"
4 f-<
(a) li+ ii (+ -i + i i + n ii liili- l+i i =+-i t i l+ =ni-i -i + i i + +ii ti -i t
(b) li+ ii +i = -i (transmission) ii ii +t- t
(c) li+ ii + +ii ~i n -iii = i i --- ti i-i t . ~- := -iii ii ii +t- t
(d) =t=i+ -i n iin n - in <i -i nii +i l- +i-i n ~-- + +ii :n+i- +i l-ii- ti -i t
(e) li+ ii n :n + i- --+ nn niil+ +-i+ +i -ti zi- t
(f) < i + =ii :=+i lnii +n ti-i t ~i t -i= +i - nii + i< -n ti i-i t
(g) li+ ii tn zii o -i + ,ii --- ti -i t t -i n iin n - in :n + i- + ,ii -ti
1.1.2 sfi+ sii + v+i (Types of inductive effect)
(a) I sii =ii =n t i :n + i- + -i zi +i ~-i ~i ~i+li - +- t . I =n t -ii :- =n ti ,ii ---
ii I ii +tni-i t + z =n ti nii ~i + I ii (:n + i- ~i+ii li+ ii) + =in +i i-i t ~i +n
l---lnli- = <lzi- l+i ni t
> > > NO
2
> SO
2
R > CN > CHO > COOH > F > Cl >
Br > I > OR > OH > C CH > NH
2
> C
6
H
5
> CH = CH
2
> H.
"manishkumarphysics.in"
2
CHEMISTRY
(b) + I sii : =ii =n t i :n +i- + -izi +i l-+li- +- t . + I =n t. -ii :- =nti ,ii --- ii
+ I ii +tni-i t
> > (CH
3
)
3
C > (CH
3
)
2
CH > CH
3
CH
2
> CH
3
> D > H
-i +- <i -i ini~i (+I, I) n ii +i ti: i - (H) nii + =i -i ni-i ni t . ~- ti: i - nii ,ii ---
li+ ii zi - ni-i ni t
Ex.1 -i- l< n l-zi ,ii <lzi - t l+ NO
2
=n t (+ I =n t t . l=+ +ii t =i:+ni t += - n = e

+i ~-i
~i ~i+li - + n +i :n +i- -- -i < -i t
COOHi COO

ur +i +ia ini faa sii riai r+

Ex.2
Ex.3
-+- <i-i -<itii ,ii - t =nt :n+i- <i-i ~ii- +I =nt ti- + +ii +i- ini ~ilzi+
= +iin+ ti i-i t :=+ li- COOH=n t I ii ~ii - :n + i - ~i+ii ii + +n- +i - ini
~i lzi+ = i-in+ ti i-i t
Ex.4 (a) CH
3
CH
2
CH
2
(b)
(c) CH
2
N C

(d)
(e) (f)
(g) (h)
(i)
1.1.3 sfi+ sii + as4in
(a) yfn+fa+ +iifufn+ ni +t nt4 ui4ai +i fariii +a (In deciding acidic strength of
aliphatic carboxylic acids) :
I ii ~-ni =in (I =n t +i -l-il- + +n- l+=i ~i +i ~-ni =in ~-ni-i + n i n lz ti -i t )
+ I ii -iii =in (+ I =n t +i -l-il- + liin- l+=i ~i +i -iii =in ~ii -iii-i + n i n
lz ti -i t )
"manishkumarphysics.in"
3
CHEMISTRY
n i +iii +t i-uanit u+sai (The Bronsted - LowryDefinition of Acids and Bases) :
:= ~iiii + ~- =i ~-n <ii t i ii- <i- + -ii -ii <ii t . i i i- n ti +
~-ni =in = ni -ii = =iii =-l-i- ti -i t I = ni -ii +i -iil <i- +-i t -ii + I = ni -ii +i
~-iii -i-i t
Ex.5 (I)
Cl
|
COOH CH C H C H C H
2 2 3

(II)
Cl
|
COOH CH CH CH CH
2 2 3

(III)
Cl
|
COOH CH CH CH CH
2 2 3

(IV) CH
3
CH
2
CH
2
CH
2
COOH
V III II I I > > >
dk e Z ; vEyh; lkeF
sat+i (Explanation)
tn i-- t l+ l+=i ~i n I =n t +i -l-il- -= ~i + ~-ni =in + n i n lz +-i t n l+- li+
ii < i (distance) l-i +- ini ii t ~- - +- l= i ln+ n I =n t COOH=n t + ~li+ l-+
-l-i- t -= i ln+ n I =nt ~li+ - = ~-i ii <lzi - ++ -= i ln+ +i -i ~-ni -i-i t
Ex.6 (I) O
2
N CH
2
COOH (II) F CH
2
COOH
(III) H
3
CO CH
2
COOH (IV) CH
3
CH
2
COOH
V II I I I I I > > >
dk e Z ; vEyh; lkeF
- +- -<iti ,ii - t l+ NO
2
=n t -i I ii <lzi - +- ini =n t t ~- l+=i ~-n n :=+i -l-il-
-= =-l-i- (corresponding) ~-n +i ~li+ ~-ni -i-i t ( I ii o~-ni =in ).
(b) y+irin +i nt4 ui4 (Acidic Character of Alcohol) : ( I) ii n lz ti - ~-ni =in n l,
ti-i t :=i +i + I ii n lz ti - ~-ni =in n +ni ~i-i t
Ex.7 (a) ~-ni =in : CH
2
OH < CH
2
OH < CH
2
OH < CH
2
OH
(b) ~-ni =in : CH
3
OH > CH
3
CH
2
OH > > OH
(c) fzri iii (Dipole moment) : I ii c- = l,i ~ii i c-i t
Ex.8 : CH
3
NO
2
> CH
3
COOH> CH
3
F > CH
3
OH
(d) yf+n +iriai4a +i iif4- (Stability of alkyl carbocation) : +ii + i- e

- - -izii t ~i t +
I ii + ,ii -iii ~i I ii + ,ii ~-iii ti i-i t +i l+ +I ii + +ii +ii + i- i-in+ ~i zi
n +ni ~i I ii + +ii i-in+ ~i zi n lz ti -i t
Ex.9 -iil :

3
CH < CH
3

2
CH < H C ) CH (
2 2

<

C ) CH (
3 3
(e) +ia a n+ +i iif4- (Stabilityof carbon free radical) : +i - n +- n n+ + I ii + ,ii -iil
i-- +- t
Ex.10 -iil :
-
3
CH < CH
3
-
2
CH < CH
3
< CH
3
CH
3
(f) +iyai4a +i iif4- (Stability of carbanion is) : I ii ,ii -iii ti -i t -ii +I ii ,ii ~-iii ti -i
t
CH
3
>
CH
3
CH
2 > CH
3
CH
2
CH
3
>
CH
3
C CH
3
CH
3
"manishkumarphysics.in"
4
CHEMISTRY
1.2 aai< y uif+ sii (Resonance &Mesomeric effect)
1.2.1 sfiiii l+=i (+ llzi ~i +i <i i <i = ~li+ = --i ,ii <lzi - l+i i =+-i t l-n nii +i l-il-
=ni- ti. ~--i< +tni-i t
~- -i<i = --i( + n +i-l-+ t . n l+- i--l+ = --i n i n<i- < -i t i l+ ~- -i< = + +tni-i t ~- -i<
= + l+=i ii ~- -i<i = --i = ~li+ -iii t ~li+ -iii ~- -i<i = --i -ii ~- -i< = + + n P.E. +i ~--
~--i< -i +tni-i t ~i +i -iil ~--i< -i + ~-+ni-i-i ti-i t
Fig.1
~li+ -iii ~--i<i =--i. ~--i< =+ n ~li+ in<i- <-i t. l+ +n -iii ~--i<i =--i. ~--i< =+
n +n in<i- <-i t
Ex.11 (I)
(II)
(III)

(IV)

(V)

(VI)

CH = CH
2
1.2.2 aai< u+ (Resonance Hybrid) :- t lli-- = i = --i +i i--l+ = --i t l= l+=i ~i + ln( nii
+ =i +-i ~li+-n l-n +i in- l+ l-i lnii i =+-i t

v uqukn l ad j
1.2.3 aai< ai (Resonance Energy) :- = + ~i == ~li+ -iii ~- -i<i = --i +i -i + n ~-- +i ~- -i<
-i +t- t
Fig.2
"manishkumarphysics.in"
5
CHEMISTRY
~- -i<i = + +i ~- -i<i -i i ln+ +i = zil--+ ~i ii ln+ ti: i -i+i -ni + ni- + ~-- + i ti -i t
l kbDy ksgsDl hu
+ H
2
mRizjsd
+ (28.6 Kcal/mol)
+ 3H
2

mRizsjd
+ 3 28.6 = (85.8 Kcal/mole)
:=ln( -i- [85.8 (49.8)] Kcal/mol -i ti -i t i -i- l,-i +- (+ ln (typical) i ln+ +i -i =
+n ti-i t :=ln( -i- ~i +i ~--i<i -i 85.8 + 49.8 = 36.0 Kcal/mole ti-i t
Ex.12 + ~i +i ~--i<i =--i lnii
(a)
3 3
CH C CH CH CH
||
O
= (a)
(b) N C CH CH
. .
N H
2

= (b)
(c) (c)
(d) CH
3
O CH = CH (d)
(e) (e)
(f) :
..
O C CH
3
=

(f)
(g) (g)
(h) (h)
(i) (i)
(j) (j)
(k) (k)
+
+
+
(l) CH
2
= C = O (l)
CH = C = O
2
. ..
.
O
O C H C
2
(m) (m)
N N N
2

"manishkumarphysics.in"
6
CHEMISTRY
1.2.4 aai< + fa4 (The Rules of Resonance)
(a) =ii +-il-+n (~- -i< = --i) i--l+ n: = = --i ti -i -ilt( -<iti + ln( l+=i n ii Cnii n i -
-i -ti ti -i -ilt(
(b) ~- -i<i = --i~i +i lni- =n =ii ~- -i<i = --i~i n nii~i + -ili+ +i l-il- =ni- ti -i -ilt( -i- <i
n: =--i~i n =--i 3, =--i 1 2 +i ~--i<i =--i -ti t. +il+ =--i 3 n (+ ti:i- nii +i (+
+i - nii = < = +i - nii l-iil- l+i ni t. i ~- -i< l+i + ln( ~ni- t
(c) ~- -i< (t-:n + i- ~- -i<) n iin n - in =ii nii (+ ti -n n ti - -ilt( l== ~- -i< n ~ii l- ti - in
+-i+ ~i= n =ni-i-- ti

i.e.

z
(d) =ii +-il-+n =--i n =ni- =i n ~ln- :n+i- ti- -ilt(
(e) i--l+ ~i +i -i l+=i ii < = = +n ti -i -ilt( :=ln( l-ii-i+i (+ -iil c i- ini i-i t
(f) =ii ~- -i<i = --i +i i--l+ ~i n i n<i- i -ti ti -i t uu fri+ ii4t uai +i 4in<ia aai<t
u+ fri+ riai r+
1.2.5 aai<t =s +i anai-+ iif4- (Relative stability of the canonical form)
(a) rit4(aifzia) uai fri+ ii4t : ~i zi i++i -iil n +ni ni-i t <i li- ~i zii + i++i
+ ln( -i +i ~iz+-i ti-i t ~- =--i l-n li- ~izi -l-i- ti- t. + i++i + ln(
~li+ -i (~ii - +n -iil) +i ~iz+-i ti -i t . ~ -ii+ - -- = --i~i +i l-n l+=i ii +i +i +i : ~i zi
-l-i- -ti ti-i
CH = CH Cl
2
CH CH = Cl
2
::
::
::+
( ) I ( ) II
(b) = --i( l-n -l-i- =ii nii ~i + = i +-i +i zi :n + i- = i i t ti - t . lzi i = -iii = --i(
ti-i t -ii = + l-ni i n ~li+ in<i- +-i t
Ex.13
CH O CH
2 3
CH = O CH
2 3
+ + :
::
( ) I
bl dkcZu esav kB
by sDVkWu gSA
bl dkcZu esa
d soy N%by sDVkWu
gS
( ) II
(II ~li+ -iii t I = )
Ex.14 CH C = O
3
+
..
..
I

(II ~li+ -iii t I = )
"manishkumarphysics.in"
7
CHEMISTRY
(c) =--i l-n ~li+ =t= ii -i ti- t . ~- =--i +i -n-i n i<i -iii =--i ti-i t
CH = CH CH = CH
2 2
( ) I ( ) II ( ) III
; g l aj puk v f/kd LFkk; h
gSD; ksafd bl esav f/kd
l gl a; kst d ca/k gSA
CH CH = CH CH
2 2
+ ::
CH
2
CH
2
CH = CH
+
(d) ~li+ l -+ii nii ~i -l-i- +iin+ ~i zi ~i +n l -+ii nii ~i -l-i- i-in+ ~i zi ~-
=--i +i -n-i n ~li+ -iii ti-i t
Ex.15 (II ~li+ -iii t I = )
Ex.16

(I ~li+ -iii t II =)
1.2.6 fuif+ sii (Mesomeric effect)
ln=i n l+ ii (+ -iii ii t l=n t :n + i -i +i nn- t n-i = nii i t n-i = (+n -i i
(+i+i n = (+n -i n ti -i t
Ex.17
ClCH=CH
2
+i I ~i II ~--i<i =--i t
t ii n - l,-i + = ni --zi n -l-i- ti -i t :=ln( t ii = ni ii ii +tni-i t
Ex.18
1.2.7 u4a (Conjugation) :- l< n nii i =nt ~=--- +n + =ii =n- n +tni- t l<
(i) t n-i +i (+ nii (+n -i ,ii l-i- t
(ii) t -i. i-in+ ~i zi. +iin+ ~i zi. lin :n + i- i (+i+i n :n + i- i-i ti
(a) CH
2
= CH CH = CH
2
(C = C ~i C = C + n =n-)
(b) CH = CH CH
2 2
+
(i-in+ ~i zi ~i C= C+ n = n-)
(c) CH = CH NH
2 2
. .
((+i+i n :n+i- ~i C = C + n =n-)
(d) CH
2
= CH
2
H C
-
(lin :n+i- ~i C = C + n =n-)
(e) CH = CH CH = CH CH
2 2

(+iin+ ~izi ~i C= C+ n =n-)

1.2.8 fuif+ sii + s+i (Type of Mesomeric effect) <i +i + ti - t
(a) + m ii (b) m ii
(a) riai-+ fuif+ sii (+ m ii) : =n t = ni - zi +i :n + i - <i- +-i t -i t +m ii <zii -i t
"manishkumarphysics.in"
8
CHEMISTRY
Ex.19 (I)
(II)
H C = CH CH = CH NH
2 2
. .
H C CH = CH CH = NH
2 2
- +
(III)
(IV)
(V)
(VI)
=n t i '+ m' ii <zii - t
> NH
2
> NHR > NR
2
> OH > OR >
O
||
R C NH >
O
||
R C O > Ph > CH = CH
2
> F >
Cl > Br > I, N = O.
(b) wii-+ fuif+ sii ( msii) : =n t l-+i = ni --zi = :n + i - +i ~-i ~i ii -- +i l- ti -i
t . m ii <zii - t
l--- =nt - m ii <zii- t
NO
2
> C N > SO
3
H > CHO >
O
||
R C >
O
||
OH C
Ex.20
Ex.21
O N = O:
. .
+
O N O:
. .
. . +
+
O N = O:
. . +
Ex.22 H C = CH C N:
2
+
H C CH = C = N:
2 . .
"manishkumarphysics.in"
9
CHEMISTRY
Ex.23 l--- ~i ~i +i ~- -i<i = --i -i+ t ai- +i l+ t ( =nt +i ii + m i m +i t `
,
Sol. (a)
3
CH C NH
||
O
(+ m =nt)
NHCCH
3
O
NHCCH
3
O
NHCCH
3
O
NHCCH
3
O
NHCCH
3
O
(b) CCH
3
O
( m ii =nt) :
C
O CH
3
C
O CH
3
C
O CH
3 C
O
CH
3
Note:
1. +m =n t -ii m =n t (+ < = = n il-il- ti -i (+ < = + =ii = n- n -ti ti - t n l+- -i-
n + =ii = n- n ti- t
etc.
2. +m =nt -i- n :n + i- i- ci- t l+ m =nt :n+i- i- ii- t
Ex.24 l--- iln+i n :n+i- i- +i +n -i:
(a)
Ans. III > I > II > IV
(b)
Ans. I > II > III > IV
"manishkumarphysics.in"
10
CHEMISTRY
(c)
Ans. IV > I > III > II
1.2.9 sfi+ i fuif+ sii + r4 -a (Difference between Inductive and Mesomeric effects)
i zsj f. kd i zHkko fel ksesfj d i zHkko
(1) ; g l ar `Ir ; kSfxd vkSj vl ar `Ir ; kSfxd esai k; k
t kr kgSA
(1) ; g vl ar `Ir ; kSfxd esaeq[ ; r ; kl a; qXehr U=kesa
i k; kt kr kgSA
(2) bl esafl XekcU/kdsbysDVkWu Hkkx ysr sgSA (2) bl esat cU/kdsbySDVkWu vkSj v; qfXer bySDVkWu
; qXe Hkkx ysr sgSA
(3) bl esabysDVkWu ; qXe FkksM+kl kvi uhfLFkfr l s
foLFkkfi r gksr kgSbl fy, vkaf' kd vkos' kmRi Uu gksr k
gSA
(3) bl esabysDVkWu ; qXe i w. kZr ; kLFkkukUr fj r gksr kgS
bl fy, bl esai w.kZr ; k/kukRed vkSj i w. kZr ; k
_ . kkRed vkos' kmRi Uu gksr kgSA
(4) ; g FkksMhl hnwj h(quite short distance) r d gh
LFkkukUr fj r gksr kgSAJ`a[ kykesar hl j si j ek. kqdsckn
; g i zHkko ux. ; gkst kr kgSaA
(4) ; g nwj hi j fuHkZj ughadj r kgSA; g J`a[ kykesa
mi fLFkr l a; qXeu ds, d fl j sl sr Fkknwl j sfl j sr d
LFkkukUr fj r gksr kgSA
1.2.10 4 f-< (Important points) :
(a) l< l+=i = ni l-il- (+ = ~li+ t i -l-i- ti - t -i + n (+ t i ti = n- n iin n -i t
CH C CH CH
2

=
+
<i t -i n = + n (+ t -i = n- n iin n-i t
(b) l< l+=i =ni l-il- (+ = ~li+ (+i+i n :n+ i- -l-i- t -i +n (+ (+i+i n :n+i-
=n- n iin n-i t
CH = CH O CH
2 3
. .
. .
+
<i (+i+i n :n +i- n = +n (+ (+i+i n :n +i- iin n-i t
(c) l< l+=i =ni l-il- t i ~i l--- n = +i: ti :-
i-in+ ~i zi
+iin+ ~i zi
lin :n +i-
(+i+i n :n +i-
- + n = n- n t i iin n - t
N
. .
+
-i:i- + i= t i ~i (+i+i n :n+i- <i-i -l-i- t nl+- =n- n +n t i iin n-i t
(d) +iin+ ~izi ~i (+i+i n :n+i- 2t :n+ i- +i -t ti +-i t l< t i + = n- n ti
2t :n+i- +i -t ti
C = CH NH
2
H
2
. .
2t :n+i- +i -t ti
"manishkumarphysics.in"
11
CHEMISTRY
1.3 fau4a (Hyperconjugation)
1.3.1 sfiiii (Definition) :
l< (+ +i - l= +n = +n (+ ti:i - nii ti (+ ~= --- nii . = = n- ti , ~ii :n +i- +-
nii . n +-n n+ ~ii :n + i- + ~ ln- +-i+ +- nii = i -ii -i t l-ii-i+i n ii iin n -i t
:= +i +i ~--i< ~l-=n- +tni-i t
iz4+ zia : +n = +n (+ ti: i - nii = - -- +i - -l-i- ti -i -ilt( i l+ (l-+-. (-+i:-. +i i-i-.
n+-n n+. -i- n + ol-il- ti
1.3.2 y+ta fau4a (Hyperconjugation in alkene)
1.3.3 +ii+ai4a fau4a (Hyperconjugation in carbocation)
1.3.4 a n+ fau4a (Hyperconjugation in radical)
1.3.5 ainra fau4a (Hyperconjugation in toluene)
(a) := +i + ~--i< + +ii :n+ i- +i l-ii- ~l-= n- ii +tni-i t
(b) := ~--i< + +ii +-il-+n n H ~i C + n l+=i +i +i -i -l-i- -ti t :=ln( := l-i
-i +i ~- -i< (No Bond Resonance) ii +t- t
(c) t ~--i<i =--i( t =ni <-i t l+
(i) C H i n + z ~il-+ n-ii -l-i- ti- t
(ii) C = C l, i n (+n i n-ii i i- t
(d) ~l-=n- + +ii ~--i< =--i +i =i = o-ti:i- +i =i + 1 ((ln+l+ n)
"manishkumarphysics.in"
12
CHEMISTRY
Ex.25
l aj puk
l a; qXeu l aj puk dhl a[ ; k
CH CH = CH
3 2
CH CH = CH
3 2
CH
2
CH = CH CH
3 3
CH
3 4
2
3
6
7
CH CH
3 2
+
+
3
4
H C C CH
3 3
CH
3
9
10
o- gkbMkst u dhl a[ ; k
1.3.6 fau4a + as4in (Application of hyperconjugation) : -
(a) y+ta +i ii4t- ~l-=n- ii + ,ii (-+i- +i -iil =nnii i =+-i t (-+i- +i -iil
~l-=ni =--i~i +i =i
~li+ ziili- (l-+- ~li+ -iii ti -i t
(b) ririat+i ai (Heat of hydrogenation) o ti:i- +i =i ~li+ ti- (-+i- +i -iil
~li+ ti -i t ~l-= n- ~li+ ti - ti:i-i+i -ni +i ni- +n ti-i t
(-+i- +i -iil

~l-=n- =--i +i =i


kstuhdj.k gkbM H
1
A
=ini--i oH +i =i ~l-= n- = --i +i =i + i ti-i t ~l-=n- = --i +i =i l--i ~li+
ti ni (-+i- ---i ti ~li+ -iii ti ni ~li+ l--iii (-+i- ~li+ -iii ti -i t
Ex.26 CH
2
= CH
2
> CH
3
CH = CH
2
> CH
3
CH = CH CH
3
(AH
ti: i -i+i
)
(c) -ri nir (Bond length) :- -i n-i: ~l-= n- + ,ii iil- ti -i t
Ex.27

(a) C II C III i +i n-i: ~-ni- = +n ti-i t
(b) C II CI +i -i n-i: ~- ni- = ~li+ ti-i t
(c) C H i +i n-i: ~- ni- = ~li+ ti -i t
(d) f&ri iii (Dipole moment) ~l-= n- + +ii ~i zi --- ti -i t ~- t ~i + l,i ~ii i +i
iil- +-i t
Ex.28 (I) CH
2
= CH
2
< CH
3
CH = CH
2
(l,i ~iii)
(II) H CH = O < CH
3
< CH
3
CH = CH H (l,i ~ii i )
"manishkumarphysics.in"
13
CHEMISTRY
(e) +ii+ai4a +i iif4- (Stability of carbocation) :- Sp
3
+i- o ti:i- +i =i ~li+ ti-
+ii + i- +i -iil ~li+ ti -i t
Ex.29 (a) < CH
3
< CH
3
CH
3
< (CH
3
)
3
(b) CH
3
> CH
3
CH
2
CH
2
> >
CH
CH C
CH
3
3
3

( li+ ii ~i ~l-= n- +i liini ii)

(f) a n+ +i iif4- (Stabilityof freeradical) o- ti: i - +i = i ~li+ ti - +i - n +- n n+ +i
-iil ii ~li+ ti -i t
Ex.30 (a) < CH
3
< CH
3
CH
3
< CH
3

(b) CH
3
> CH
3
CH
2
> >
( li+ ii ~i ~l-= n- +i liini ii)
2. n i +ii (Acid and Base)
2.1 (a) n i +ii +t i-uanit u+sai (Bronsted-LowryDefinition) :
:= ~iiii + ~- =i ~-n <ii t i i i - <i- + -ii -ii <ii t . i i i - n ti + := ~iiii +i
tn l--- -<iti ,ii =nn =+- t
n=i ti:i -+ni i: (HCl) +i n n ln l+i i-i t -i l--- ~lil+i =--- ti-i t
- +- ~lil+i n ti: i -+ni i:. (+ ~-- -i ~-n t . ~- :=+i i i- n +i -ii-i--l- ti i-i t -ii
n i l+ (+ -ii +i ii l- ti <lzi - +-i t := i i - +i n ti + n -i t l=+ +n- ~lil+i + -i--
-i< + n ti: i l-n ~i- (H
3
O
+
) -ii +ni i: ~i- (Cl

) i-- ti - t ~lil+i = - t l+ l+=i ~-n

+ ii- <i- +- + z-i- i ~i i ~i- --i t. t -= ~-n +i = ln- -ii +tni-i t :=i +i l+=i
-ii + i i- +i n ti +- + z-i- i ~i i ~i- i-- ti -i t t -= -ii +i = ln- ~-n +tni-i t ~-
-i +- ~lil+i n Cl, ti: i - +ni i: (HCl) ~-n +i = ln- -ii t -ii H
3
O
+
, n (H
2
O) i l+ ~lil+i n -ii
+ n +i +-i t . +i = ln- ~-n t
(b) n y +ii +t nru u+sai (The Lewis Definition of Acids and Bases)
n:= + n-i-=i ~-n (+ :n+i- n niti -ii -ii (+ :n+i- n <i- +- ini ti-i t ~- n:= +i
~-n-ii iiii + ~- =i + n i i - <i- +- in <ii ti ~-n -ti ti - - ~- +: +i + <ii ii ~-n
i -ii ti =+- t
-<iti + ln -i- <i ni ~lil+i~i +i ~- + -i ai- ti -i t l+ (n lnl-n +ni i:. ~ni l-i = -=i +i
~lil+i +-i t . l= +i (+ i i - <i-i =n t +i ~ni l-i = ~lil+i =--- ti -i t . l--- <i -i ti ~lil+i~i
n ~nil-i :n + i- n <i-i (n := -ii) +i ii l- ti <lzi - +-i t
Cl + H
"manishkumarphysics.in"
14
CHEMISTRY
2.2 riri+iai +t uisf+i+ nt4 ui4 (Relative acid strength of different hydrocarbons)
(ii:- n sp = +l- +i - nii + ~li+ l - +ii ti - + +ii :=+ C H i n ~li+ i i --- ti i-i
t . l=+ +n- :== H nii ~li+ i-i zi ~i i- = =n-i = (ii:- ~i := in < -i t -ii -i
~-ni ti <lzi- +-i t
HC CH > H
2
C = CH
2
> H
3
C CH
3
2.3 f+ain (Phenols)
l+-i n + ~i-i+i ,ii i-- l+-i +=i: ~i-. l+-i n = ~li+ -iii ti -i t . +i l+ l+-i n +i ~ -ii l+-i +=i:
~i- ~- -i< ,ii ~li+ -iii+i i-- +-i t l+ l+-in n li--li-- ~i zii +i -l-il- = t +n -iii
ti-i t -+- -i +i l--- ~--i<i =--i~i ,ii - l+i i =+-i t
=nt i I, -ii m ii <lzi - +- t . + l+-in n = ti - + +n- t l+-in +i ~-ni =in
+i c i- t . +i l+ :- =n ti +i -l-il- = --- ii ~- -i< + ,ii +ii zi + l-ii-i+i +i ~i ~li+ c i-i
t :=+ li- + I -ii + m <lzi- +- in =nt l+-in + ~-ni =in +i +n +- t
Ex.31
(l+=in)
~-ni =in +i +n = I > II > IV > V > III
a4 I : i ln+ III ~-- < n ~-ni ti <lzi - +-i t . +i l+ :=n +iin+ ~i zi +i l-ii-i+i -ti ti
i-i (nii ii ~- l-i-)
a4 II : I, m <lzi - +- in =nti +i -l-il- l+-in +i ~-ni =in ci-i t . ~- -i: i l+-in. l+-in
+i ~ -ii ~li+ ~-ni t
a4 III l+=in ~i n ii+=il+-i n +i ~-ni =in +i ~- + -i ai- ti -i t l+ n ii+=il+-i n n OCH
3
=n t
+ + m ii + +n- n + :n + i- i- +i ni- c i-i t l== -=+i ~-ni =in-i i-i t
Ex.32
~-ni =in +i +n I > III > II > IV
-i+- -<iti n iln+i + ~-ni =in + +n +i l--- -i ,ii =nni i =+-i t
a4 I : CH
3
+ I ii i-i t :=ln( =ii n linl+-in (l+=i n) l+-in (I) +i - -i-i n +n ~-ni ti -i t
a4II : l+=in n i ~i ~i ii CH
3
~l-= n- + +ii e

i- ci- t n l+- ~i ii =nii n +I ii ii

nn-i t i l+ l+-i+=i: ~i- +i ~-iii +-i t :=ln( ~iii == +n ~-ni ti -i t
- l+ ni l-il- +I +i +-i t ~- t l+=in n == +n e

i- i-i t :=ln( ~-ni-i +n n l,-i

-ii- ti-i t
"manishkumarphysics.in"
15
CHEMISTRY
Ex.33
~-ni =in +i +n II > IV > III > I
a4 I : -i:i l+-in n NO
2
+i I ii ~-ni =in +i ci-i t :=ln( =ii -i:i l+-in n l+-in == +n
~-ni ti -i t
a4 II : n i -i: i l+-in n + n I ii ni- (applicable) t ~ o, p <i -i n NO
2
+i I, m ii nn-i
t := llzi l-il- n P =nii O=nii +i - n-i n ~li+ ~-ni ti -i t
2.4 +iifufn+ ni +t nt4ai (Acidityof carboxylic acids) :-
R C OH
O
-
R C O
O
(I)
+

H
(i)
-
R C O
O
(I) <i - -i+i ~- -i<i = --i( I - (A) -ii I - (B) n ~l-- i-i t t ~i- ~- -i< ,ii -iii
ti-i t ~i ~--i<i =+ =--i I - (C) t
-
R C
O
O
I(A)
-
R C
O
O
I(B)
R C
O
O
I(C)
(ii)
-
R C O
O
~i- ~- -i< + +ii ~li+ -iii ti -i t . ~- +ii l+=ln+ ~-n +i + l- ~-ni ti -i t
(iii) - l+ :n + i- ~i+ii =n t (I ii) +ii l+=n ~i- + -iil +i ci- t . ~- :-+i -l-il- = ~-ni-i
n lz ti -i t
C
O
O
X
Ex.34 F CH
2
COOH > Cl CH
2
COOH > Br CH
2
COOH > I CH
2
COOH
Ex.35 Cl C COOH
Cl
Cl
> Cl CH COOH
Cl
> Cl CH
2
COOH > CH
3
COOH
"manishkumarphysics.in"
16
CHEMISTRY
(iv) - l+ :n +i- l-+ii =n t (+ I ii) +ii- + -iil +i +n +- t . ~- ~-ni =in i-i t
C
O
O
X
Ex.36 HCOOH> CH
3
COOH> CH
3
CH
2
COOH
Ex.37
COOH
COOH
>
COOH
COOH
CH
2 >
CH
2
COOH
CH
2
COOH
iii sii (orthoeffect)
t =ini- -ii t l+ o =nii ~-n :=+ < = =nii ~i - +ii l+=ln+ ~-n +i - n-i n ~li+ ~-ni
ti -i t t -i :+ ~-n +i ~iii ii +tni-i t l+ :=+ ~i< ii t
~-ni =in +i +n II > IV > III > I
~- ~i ii =nii ~i ii ii + +ii == ~li+ ~--ii ti ni
Ex.38 (1) (G = m, I)
K
a
+ = iii > si > ai > -ir+ n
(2) G = (I > +m) Cl, Br, F, I
K
a
+= iii > ai > si > -ir+ n
(3) G = (+m > I) ..... OCH
3
K
a
+= ai ~ iii > -ir+ n> si
"manishkumarphysics.in"
17
CHEMISTRY
(4) G = (+I, H.C.) ........ R (yf+n ur)
K
a
+ = iii > -ir+ n > ai > si
Ex.39 <i 4iffa4 ui4f4i nt4 ui4 +i anai-+ r44a
(Comparison between two geometrical isomers)
1. nn:+ ~-n +nl+ ~-n
~- K
1
m
> K
1
f
n n :+ ~-n n i i- <i- +- + z-i- :=+ = ln- -ii +i ~-- ~iil+ ti: i - i ,ii -iii+i ti i-i
t l+-- n n: ~i- ,ii - (+ ~i +i in +- + +n- <i =nt l-zii-=i (+<= +
=in- ~i i- t . ~i =- i - zi +i ~-iii -i < - t l+ +n ~i- n t l-+i i ~-- - --n ti- +
+ii K
2
f
> K
2
m
ti-i t
3. +iit4 ui4 (BASES)
3.1 yfn+fa+ +ii (ALIPHATICBASES)
l+=i ~i +i ziii ( =n-i = ii-i+i ( ii- n iti l-i) ti -i. -=+i -iii + l- +i <lzi - +-i t
lli-- -i: i - +- -iii +i -iii =in +i =ini-- --+ ,ii ziii ( =n-i = i i- n ti +- + ~iii
<ziii i-i t ~ tn -i- l< n + z -i: i - +- -iii +i -iii =in +i ~- +- t
, , ,
- +- ~i ~i n -l-i- n lin =n t ( Me) + + I ii + ~iii :-+i -iii =in -i +i +n l---i- =i ti -i
-ilt
NH
3
< MeNH
2
< Me
2
NH < Me
3
N i i--l+-i n i-- -ti ti -i t
+i l+ l+=i ii (ni- +i n n -iii =in -i + n -=n -l-i- -i: i - nii +i =n-i = :n + i - <i- +-
+i l- (i i -i+i) ,ii ti l-ii l- -ti ti -i l-+ +z ~- +i+i = -i: i - + i= iii =nti +i (+lzi-
ti -i. lziln ii. lni+i+i i ni - ~il< ii :-+ n ii +i iil- +- t
"manishkumarphysics.in"
18
CHEMISTRY
(l-+n =n t +i ~i+i c - lziln l-+i i ii c -i t ~- ~ni l-i + n-n -ii ti - -+ -iii =in c -i
t =ii ~nil-n ~i-i ( ii- - + i< i-i-) n i-i zi ti-i t -ii lni+i+i i ni - + +ii
-iii+- ti i- t ~i- +i ~i+i l--i ~li+ tini. lni+- ---i +n tini (l-+n =nt +i i ii
lni+i+i i ni - ,ii i lziln iii + ,ii =ni-- l+i i =+-i t l,-i+ = - -i+ (ni-i -+ i-
(+n n +i -nli c-i t . l+-- i-i- :--i i ti i-i t l+ t +n lni+i+ - ti -i t :== ~i-
+i -iii+i ii i-i t -ii -iii+i n +ni (l-+n =n t + ii = ~li+ ti -i t ~- (+n n +i i i -i+i
+ ln ~li+ -ni +i- t
>
~- - +- <i li- iii . i-i- +i lni+- (solvation) ( + I iii + liin- - +- -iii +i -iii
=in-i l---i-=i +n n i-- ti-i t
Me
2
NH > Me NH
2
> Me
3
N > NH
3
ti (+ i- i- < - i t l+ - +- -i: i - +- -iii +i -iii =in +i +n n = ~-ii n lnli- ti
t-i t . ll-- -ti ti -i
Me
3
N > Me
2
NH > MeNH
2
> NH
3
+i l+ n = ~-ii n + n +I ii ti ~i +i -iii =in +i l-ii i +-i t . ti lni+- ii -l-i- -ti
ti -i t
uia =s u : (lin(ni- +i -iii =in -i +i ii l--- +i <lzi- l+i i =+-i t
Et
3
N > Et
2
NH > EtNH
2
> NH
3
(n = ~-ii)
Et
2
NH > Et
3
N > EtNH
2
> NH
3
(n lni+ + n )
3.2 yifa+ yta (Ph
:
NH
2
) 4i yfanta (Aromatic amines (Ph
:
NH
2
) or Anilines)
~ li- ((+i+i) n t n-i + =ii = n- n t-i t, t 2p nii +-i+ n t-i t , :=ln( t ~--i<i
-iii+i ti =+-i t
(l-ni- NH
3
- n-i n < n -ii ti-i t +il+ t l-ii-i+- (+i+i e

n i-i t
Ex.40 l--- n = +i - ~li+ -iii t
li n ~i n -l-i- (+i+i :n + i - n (lone pair) + ~- -i< l+i n iin n - + +ii t < n -ii +i -t ti
<lzi - +-i t l+ lll- n (+i+i :n + i- n t +-i+ + n-- -n n -l-i- t-i t l== t ~- -i<
n iin -ti n -i -ii =n-i = l+=i ii- ,ii nti +- + ln -ni t-i t
"manishkumarphysics.in"
19
CHEMISTRY
Ex.41 l--- n = +i - ~li+ -iii t ?
CH
3
NH
2
l+=i ii ~i n -l-i- Nnii ,ii =n-i = (+i+i :n + i - n +i <i- +-i -=+i -i -iii + l- +i <lzi -
+-i t . - +- <i -i ~i ~i n CH
3
NH
2
~li+ -iii ti ni +i l+ CH
3
=n t + + I ii + +ii. N -l-i-
(+i +i :n +i- n =n-i = <i- +- + ln -ni t-i t :=+ li- (ln(ni- ((-iln-) n -i: i-
-l-i- (+i+i :n +i- n ,ii ~--i< l+i n iin n- + +ii. t <n -iii +l- <zii-i t
~i ii l--iii G+i lziln ii (~i ii ii)
H N:
2

G


H
H N H

G
+

H
(a) ~iii - l--iii (l-ni- - (l-ni- +i -n-i n <n -ii ti- t
(b) ~iii - l--iii -i< ( =ni ~-n ~ii- i-i-) + lni+i+i n lziln iii ---i +-i t
(c) zi =nt = NH
2
~i OH zi =nt + +ii t ii (SIR) -ti <zi- t.
Ex.42 (1) G = (m, I); NO
2
(a) (b) (c) (d)

NH
2
((-ini- > m > p > o).
(2) G = (I); CCl
3
CCl
3

NH
2

CCl
3

NH
2

CCl
3

NH
2

NH
2
((-ini- > p > m > o).
(3) G = (I > +m); Cl
Cl

NH
2

Cl

NH
2

Cl

NH
2

NH
2
(-ini- > p > m > o
+n (I) +n l-iil- +-i t
(4) G = (+I, HC); l< R = CH
3
(in:i-=)
CH
3

NH
2

+I
m

NH
2
(5) G = (+m > I);
K
b
+n : P > (-ini- > O > M
"manishkumarphysics.in"
20
CHEMISTRY
4. fif+4i r4at y ni4ai
4.1 uru4i+ ri ri f<na {fia)
uru4i+ ri +i fiizi i uizi ri fia
+i l-+ i ln+i n lli-- ~lil+i( i =t= i + i + -- i li- ti - + +n- =--- ti -i t =ni--
=t= i+ i +i li- n = <i +i = ti -i t
=t= i+ -i + l-i- :n + i-= <i -i l-i- nii~i n = l+=i (+ nii i -i -n i- t . l=+i
l - +i-i ~li+ ti -i t . := +i + i li- +i lini zi li- +t- t := i li- = ~i-i +i l-ni i
ti -i t
~- < = +i +i i li-. l=n l-i- :n + i- <i -i nii ~i =ni- = l-l- ti - t . -i ( = i +i
=ni zi i li- +t- t := i li- + +n- n +- n n+ i-- ti - t
lini zi i li- + ln ~i n i +i i l- ti -i ~iz+ t
-ii l+=i ii i +i i i-i -= -i + ,ii t nii ~i +i l -+i-i~i n ~-- + +ii --- ti -i t
i + ,ii t nii ~i +i l -+i-i~i n l--i ~li+ ~-- ti ni. t i ---i ti ~li+ i l- ti ni - +-
-<iti n B +i l-+i-i A+i ~ -ii ~li+ t
i i l- i ti - + z-i- ii lini zi li- = i -ti ti i-i. :=+i n +ii t l+ lini zi li- = --
in <i -i ~i zi li- ti - + +ii (+ < = +i ~i+li - +- t- t . l== --+i i i i++i -ti ti i-i
+i l+ i i i++i + ln ~l i+ -i +i ~iz+-i ti -i t ~+= lini zi li- +i ( = ~i ,ii l-
l+i i-i t l-n ~l-i- n (unshaired pair) -l-i- t-i t . -ii i ~li+i+ + nii = = i - ti + -i
i l-ln - +-i t
- i + l-ni i + ,ii ti + z -i i lini zi li- + ln ~iz+ ti -i t . -ni +ii i-i t
4.2 +iwii4a (Carbanion) :
sfiiii : (+ +i - n-i l=+ i= -i- -i n ~i (+ +iin+ ~izi ti. +i (-i- +tni-i t
Ex.43 , nlin +i(-i-
Ex.44 CH
3
(lin +i(-i-
Ex.45 (CH
3
)
2
~i:=iiln +i(-i-
u+i : +i(-i- +i =+i sp
3
, sp
2
~i sp ti =+-i t
u+i a<iri
sp
3
, CH
3

sp
2
H
2
C = , CH
2
= CH
sp HC
"manishkumarphysics.in"
21
CHEMISTRY
+iyai4a +i iif4- :
+i -(-i- :n+i- ~i+ii =nt + ,ii -iii ti- t
(i) I ii (ii) m ii (iii) ~i zi +i l-ii-i+i
+i +ii- (+i (-i-) n : = -iii (:n+i- <i-i) +i iil- ti <lzi - +- t :-n :n + i- +i i- ~li+
ti - + +ii :-t -ili+ -- ti ii +t- t ~- :n + i - i- ~li+ ti - + +ii lli-- ~lil+i~i ,ii :n + i -
--ti ~i+ni + :n+ i- n +i <i- + ~- +iin+ ~i zi +i -<i=i- -i- +i +ilzizi +- t
Ex.46 CH
3
>
CH
3
CH
2 > CH
3
CH
2
CH
3
>
CH
3
C CH
3
CH
3
(-iil +n)
Ex.47
2 2
H C CH CH
O
= <
2 5 6
H C H C
O
<
O
C ) H C (
3 5 6
(-iil +i c-i +n)
ni4ai (Tautomerism) :
sfiiii : -ni-i t l+i t. l=+ ~--n - (+ ti i ln+ +i <i i ~li+ (=i = --i( i l+ (+< = n
ziii -i = ~-- ll- - ti -ii l-n +n = +n (+ nii + -ili+ =ini-- ti: i - nii +i = li- -ii(
li--li-- ti
+tai y rain ni4ai
+ii l-n i ln+i n +ii ( :-in (+ lzi i +i + = --in+ =nili (constitutional isomers) +i ii l-
ti <lzi - +- t <i -i =nii (+ii ( :-in ) l+=i ~-n i -ii +i -l-il- n =n-i = (+ < = n
~-- ll- - ti - t- t ~- -i +- <i -i ~--ll- - i (+ii ( :-i n ) +i -nii -ii ~-- l- -
+i -ni-i + -in = liili- l+i i-i t
~li+i zi lzi i ll-il-i n +ii ( : -i n =i-i-ii (equilibrium) n ti - t (=ini-- +ii :-i n -ni-i
(l-ti: ( +ii -i n - ti ti =+-i t . :-n +n = +n (+ o-Hnii ti ni -i +ii l-n i ln+i = (=ii -
( (l= l-ti: n =i- ~-ii n :-i n +i nizii +ii +i ~ -ii ~-- +n ti -i t . = (=ii - n l< < ii
i -i : -i n +i nizii 1%= ii +n ti -i t ~- ni -i +ii l-n i ln+i n +ii + ~li+ -iil +i n +ii
: -in n -l-i- +i -+i - t i +i ~ -ii +ii n -l-i- +i -~i+=i- t -i +i ~li+ =in +-
ti-i t ( ~ 364 versus ~ 250 kJ mol
1
):
+tai=s rain =s
(l=l-ti:
(=ii -
=i:+nit+=-i-
"manishkumarphysics.in"
22
CHEMISTRY
~ l< tn -- ~i~i +i ~- + l-n <i +iil-n =nt ti -ii i (+ CH
2
=nt ,ii i++- ti (|-
i:+ii l-ni ln+ +tni- t ) -i tn ai- ti -i t l+ :- ~i ~i n =i-i-ii :-i n +i l-zi- nizii ~-- ---
ti-i t -<iti + ln ---2, 4 -i: ~i- + < n :-in +i l-zi- nizii 76%ti-i t
~- |-i:+iil-n iln+i n :-in + ~li+ -iil +i +ii :=+ ~i n =ln- l,-i +i ~--i< ,ii
-iii+i -ii ~i n ~--i~il+ ti: i - i ,ii (-l+ = --i) +i --i t l= l--- +i = <lzi- l+i
i =+-i t
+iil-n iln+i +i :=+ :-in n l-- :-ini:zi- (enolization) +tni-i t
n an fa a i :
N
|
H
O
O
N
O
OH
C
||
O
SO
2
NH
C
|
OH
SO
2
N
airaiyutairai ai :
-i: i iln+i +i ~-ni =in +i ~- +- ai- ti-i t l+ -i:i i ln+ <i i n lnn- t (+ ~li+
-iii =ini- -i:i ( <=i +n -iii (=i-i:i
R CH
2
|
N
O O
ukbVks: i
-i:i . (=i-i: i +i ~ -ii ~li+ -iii ti -i t +i l+ t ~- -i< ,ii -iii ti -i t
Ex.48
C H CH N
6 5 2
O
O
ukbVks: i
airaiuiiruiairaiui ai :
iiln+ ( l,-i+ -i: i i ln+ +i -t. iiln+ ( l,-i+ -i: i =i i ln+ ii. --+ ~li+ -iii ~i:=i -i: i =i
i ~i+=in + =ii -ni-i <lzi - +- t
"manishkumarphysics.in"
23
CHEMISTRY
Ex.49
CH CH NO
3 2
ukbVksl ksi zksi su
CH CH = NOH
3
, l hVSYMksfDl e
CH CH CH
3 3
2-ukbVksl ksi zksi su
|
NO
NOH
, l hVksuv kWDl he
|
CH C CH
3 3
|
rtayaita ai :
Imine
R CH CR = NR
2
-i+- <i -nii i n. (-ini- +n ti -iii ti-i t. ti -i:i - +i: ti:i- nii -l-i-
-ti ti -i ~-ii :ni- ~li+ n (predominates) ti -i t
-asfaa +t sf+4i
(a) +iia-s+t4 raint+i -ii- +i : -i ni+i ~lil+i n-i :-in ~i- ,ii =--- ti -i t . := +i
= n-i :-in ~i- -- = ~i n o-ti:i- nii +i ~-ni-i :=+i ii -i t
-i +- ~lil+i +i l< tn ~- + -i ai- ti -i t l+ l< n + ~i ,ii i-- Hnii = :-in ~i- n
o C nii +i i i-i+i ti - +ii l-n iln+ l+ ~i+=i- nii +i ii -i+i ti- :-in i--
ti -i t ~- +ti i =+-i t l+ :-i n ~i-. +ii l-n i ln+ ( :-in <i -i + = ln- -ii +i ii l- ti
<lzi- +-i t
(b) na-s+t4 raint+i +iil-n iln+i n ~-n-+i :-ini+i l+i :-+ =ln- ~-n + ,ii
=--- ti -i t -ii i-- ~i- +i + l- +i i-i- + =ni- ti -i t -i- <i ni ~lil+i ,ii - t l+ l< = ln-
~-n +i ~i +=i- nii ~-i i i - ii -i t -i - +ii l-n i ln+ -ii l< = ln- ~-n +i o-+i - nii ~-i
i i- ii -i t -i :-i n i-- ti -i t ~- +ii l-n i ln+ ( :=+i :-in . =ni- = ln- ~-n + =nii
ti- t
(c) l+=i i ln+ n o+i - nii -l-i- ti: i - nii ~i +i ln ,ii ll-n - + n -iii ,ii - +i
= ni+i ~lil+i t l-+ -i +- l+i ~-ni ,ii ii o-+i - + - i = = i ti -i t . l= -ni-i + -in
= --nli- l+i i-i t
"manishkumarphysics.in"
24
CHEMISTRY
4.3 +iriai4a (Carbocation) :
sfiiii : (+ +i - n-i l= -i- -i n ~i (+ i-in+ ~i zi ti . +i i-i- +tni-i t
Ex.50 , nlin +ii-i-
CH
3
(lin +ii-i-
u+i : +ii-i- sp
2
~i sp =+l- ti =+-i t
u+i a<iri
sp
2
sp H
2
C = , HC
iif4- : +ii-i- l--- + +ii -iii ti- t
(i) + I ii (ii) + m ii (iii) ~l-=n- ii
+iriai4ai +t rnaia -4aai
+i i-i-i + = i +-i +i zi n + n z :n + i - ti - t . := +ii t n : = ~-ni BF
3
-ii AlCl
3
+i ii l- +i +-
t n - +i i-i-i +i i- +in (life period) -ili+ ti -i t ~- ~li+ l+iziin ti - t +i i-i- ~-i ~a+
i +- ~ii - -iii ~-ii i-- +- + ln n : = -iii (~i i :n + i- n <i- +- t ) + =ii ~lil+i +-
t
+i i-i-i +i :n+ i- - - l-i + +ii =i-+-i +i i-i-i +i :n+ i--- ti (electrophile) + -in = +i-
t =ii n : = ~-n. i i - =lt-. :n + i - -- ti +tni- t :n + i- -- ti ~li+n +i n :n + i- +i i- +n ti - +
+ii -ili+ -- ti (nucleophile) ~i+ni + ~-i ~a+ i (~l+ n =i + =ni-) + -iil i-- +- t
Ex.51 > >
t-ln +ii+i- n -i- Me =nt +i + I ii ~i ~l-=n- := ~li+ -iii -i <-i t
Ex.52
+
CH
2
csUt kbfy d
/kuk; u
>
+
, fFky /kuk; u
CH CH
3 2
>
+
foukby /kuk; u
CH = CH
2
ln i-i- n -l-i- l--- ~--i< ii i-i t i +i- i-i- +i =ili+ -iil <i- +-i t
(lin +i i-i- n lin =n t + + I ii ( ~l-= n- ii + +n- -iii ti -i t l+ l-i:n i-i- +
-iil + i- +i +ii sp
2
= +l- +i - nii + ii = li -+ii ti - + +ii I ii l<ii-i t i l+ i-in+
~i zi +i c i-i t
"manishkumarphysics.in"
25
CHEMISTRY
saf-4iu (Rearrangement)
l+=i ii ~lil+i n (+ n-i +i i-i- +i l-ni i ti -i t -i t +i i-i- ~- -iii +i i-i- n -l -i=
ti - +i l- ti -i t =ini-- =ii +i i-i- -l -il=- -ti ti - t . + n ti +i i-i- - l-i- ti - t . l-+
-l-i= ,ii (+ -iii +i i-i- +i -l-i ti
-<iti + ln l---lnli- ~lil+i~i +i ~- +- t
(a)
~lil+i (a) n +ii-i- -i --i t. l+-- -=+i -l -il=- l+i -ti ti-i
(b)
(c)
n l--i (ring expansion) t - ii +ii +i- n - l-il=- ~lil+i =--- ti -i t

(+ ~- ~li+ -iii +ii-i- =i:+ni i lnn lin +ii-i- l= -i- <lzi - l+i ni t
t lzi i ~-ii +i +i -iii+i +n -i- =<-i ini n n < ii ni t
( -i:n +i ~ -ii ~li+ -iii)
=i:+ni iln n lin +ii-i-
4.4 a n+ (Free radical)
~lil+i( l-n =t= i + i +i lini zi = li- ti -i t . -ii l-n lli-- ~li+n +. n-i i -i<.
~i-= + n ti - t . ~il-+ ~lil+i( +tni-i t
~il-+ l+illi ,ii =--- ti - ini ~lil+i~i + ~l-l+- +i l-+ =i- n (+ ~- < =i l-- - ~lil+i ii
ii =l-nln- t . l-n =t= i + i +i =ni zi = li- ti -i t . -ii := l+i + +n- ~ ln- :n + i -
+- nl-i +i -i<- ti-i t
:-ti ~ln- :n + i- n +- nl-i (intermediates) +i n+-nn+ + -in = liili- l+i i-i t
"manishkumarphysics.in"
26
CHEMISTRY
Table : 1
Ex.53 H CC
3
CH
3
CH
3
>
3 2 3 3 3
H C H C C H CH H C C H
- - -
> >
{iif4- +)
Ex.54
-
C ) H C (
3 5 6
> H C ) H C (
2 5 6
-
>
2 5 6
H C H C
-
>
3
3 2
CH
|
CH C CH CH
-
= {iif4- +)
4.5 fzu4it +ia r4at +ita (carbenes) :
sfiiii : ( = nl- i +i =n t l-n +i - nii + n <i i -i-i t := +i + -<i=i- l,= i i +i - nii
+- i ln+ +ii - +tni- t n - +ii - ~li+ ~-iii ti - t = ti l+=i ~lil+i n t -- t . - -- ti l+=i
~- ~i = ~lil+i + n - t +ii - n-i -zii +i ~lil+i( lzi i l-+ ti -i t . ~- + +i + -<itii
n t ~lil+i( lzi i = llzi lziln ~ zi (degree) +i <lzi - +-i t
+ita +i aia +t ffri4i
CHCl
3
+ : CCl
2
CH
2
I
2
+ Zn : CH
2
CH
2
N
2
N
2
| + :CH
2
CH
2
= C = O : CH
2
+ CO|
+ita + s+i
(+n (Singlet) +ii- lzin li- (Triplet) +ii -
Table : 2
, dy dkchZu f=kxq. khr dkchZu
vkd`fr
Bent (
eqM+hgqbZ
)
j s[ kh;
l adj . k
sp
2
sp
vfHkf; k f=kfoe fof' k"V dksbZugha
voLFkk mksft r voLFkk l kekU; voLFkk
(Ground state)
pqEcdRo i zfr pqEcdh; vuqpqEcdh;
i zd`fr i zfr pqEcdh; f} ewyd
(Diradical)
4.6 airata (Nitrenes) :
t (+ -<i=i- n-i -izii t . l=n (+ i n -ii <i (+i+i :n+i- n +- -i:i - nii -l-i-
ti-i t -i: i- n N nii + ~+ + ~i ti - + +n- t ~li+ l+iziin ti - t
"manishkumarphysics.in"
27
CHEMISTRY
4.7 -ira (Benzyne) :
-i:- n-i n -i- n (+ ~l-l+- C Ct i ln t ti -i t
-i:- +i -+- =--i~i + ~iii - t l+ -i:- n-i n t -l-ln- t i ~- <= t +-i+i +
=ii n +i ~- -i< l+i n iin -ti n -i t . +i l+ t i. t +-i+ + n-- -n n l-i- t-i t
-i:- i n + +i - sp
2
=+l- ti -i t l :- +-i+i + n ~l-i- :--i ~li+ iii -ti ti -i t
"manishkumarphysics.in"
28
CHEMISTRY
MISCELLANEOUS SOLVED PROBLEMS (MSPS)
1. l---lnli- ~i ~i n li+ ii (I effect ) +i -i + l--ti ,ii l-l- +il
(a) CH
3
CH = CH NO
2
(b)
Sol. (a) CH CH
3
NO
2
+o o
CH
+oo
(b)
O
-o
-o -o
-oo -oo
2. l---lnli- n ~-ni =in +i +n l-iil- +il
Sol. CH
3
COOH<ClCH
2
COOH< Cl
2
CHCOOH< Cl
3
CCOOH
3. l--- ~i +i ~--i<i =--i lnli(
, CH
2
= C = O ,
Sol.
+
+
+
CH = C = O
2
. ..
.
O
O C H C
2
,
N = N = N N N N
2

4. l--- ~i~i +i ~--i<i =--i -i+ -i: +i + m i m ii <zii- t

,
Sol. (a)
O
||
CH C NH
3 (+m =nt)
NHCCH
3
O
NHCCH
3
O
(b)
CCH
3
O
CCH
3
O
(m =nt)
CCH
3
O
C
O CH
3
C
O CH
3
C
O CH
3
C
O
CH
3
"manishkumarphysics.in"
29
CHEMISTRY
5. l--- n = +i - ~li+ -iii t `
(a) (b)
Sol. ~li+ -iii t +il+ -i:i- (+i+i :n+ i- n =n n -ti t
6. l--- n = +i - ~li+ -iii t `
(a) (b) (c)
Sol. ~li+ -iii t. +il+ -i: i- nii sp
3
=+l- t -ii (+i+i :n+i- n =n- n -ti t
7. l--- n = +i-= n n in l,-i +i -n-i n n -ii t
(A) , (B) ,
(C) , (D) CH
3
NH
2
, CH
3
OH
Sol. A, C, D
> >
8. l--- n = == +n -iii t
(A) (B) (C) (D)
Ans. A
Sol. (A) == +n -iii t . +i l+ = - -i +ii- t
9. -i - ( =i:+ni t +=-i - + (+ -nii +i lnli
Sol. (a)
H O
|
CH CH C CH
3 3
= , (b)
10. l--- +ii +i- +i -iil + +n n l-i- +il(
1. H
2.
"manishkumarphysics.in"
30
CHEMISTRY
Sol. (1) CH = CH CH
2 2
+
> >
(2)
+
>
+
>
+
Sol. (1) CH = CH CH
2 2
+
> >
(1 + ~--i<) (2 + ~l-=n-) (~--i< ~l-=n- -ti t)
(2) -iil +n : 3 > 2 > 1
11. l--- n = +i - =i li+ -iii +ii +i- t
(A)
2 2
H C CH CH

=
(B)
3
H C

(C)
H C CH CH
3

=
Sol. (A) ~--i< + +ii
12. l--- n+- n n+ +i --+ -iil + c- +n n l-i- +il(
Sol. V < III < I < II < IV
Sol. ~--i< ,ii n+- nn+ ~li+ -iii ti -i t