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Copyright © 2007, New Age International (P) Ltd., Publishers Published by New Age International (P) Ltd., Publishers

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ISBN (13) : 978-81-224-2872-8

PUBLISHING FOR ONE WORLD

NEW AGE INTERNATIONAL (P) LIMITED, PUBLISHERS 4835/24, Ansari Road, Daryaganj, New Delhi - 110002 Visit us at www.newagepublishers.com

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λ

λ=

=

 

 

π λ λ

 

rr

 

π

 

π

π λ λ   r r   ∴ π   π π Distance K L M

π

Distance K L M N O Charge Density
Distance
K
L
M
N
O
Charge Density

π

π

λ

λ

π

+

+

λ

=

=

π λ

−

λ=

= −
=

ψ

ψ

+

π

−=

ψ

ψ

+

ψ

+

ψπ +

=

ψ

π

∇+

ψ

∇+ ψ − ψ =

ψ

=

π

ψ ψ ψ ψ ψ

ψ ψ

ψψψψψ ψψψψψ

ψ ψ ψ

×

+∞

−∞

ψ

=

ψ

∂ψ

+

∂ ψ

+

 

θ

∂ψ

 

θ ∂ϕ

θ

∂θ

∂θ

+

π µ

−=

θ ϕ

m e N rr E (a)
m e
N rr
E
(a)
e m r E N (b)
e
m
r
E
N
(b)

ψ θ φ ψ θ, ϕ ( ) .

θ

Φ

ψ θ, φ ψ θ, φ

Θ (θ) . Φ (φ)

Θ

(θ)

ϕ

(φ)

θ

ψ ψ θ φ ψ

 
 

ψ

ψ

ψ

+++

π

=

ψ

 

ψ

ψ

 

     

[x]

V

V

  V=0 0
 

V=0

  V=0 0

0

x=0

 

x=L

(a)

n=1 n=3 n=2 (b)
n=1
n=3
n=2
(b)
n=3 n=2 n=1 | | 2 L 0 L
n=3
n=2
n=1
|
| 2
L
0
L

(c)

ψ ψ

ψ

ψ

ψ

ψ

Energy

π

π

π

=

π

n=3

n=2

n=1

E

E

E

0

x=0

x=L

3

2

1

Energy ∴ π π ∞ π = π ∴ ∞ n=3 n=2 n=1 E E E
∆ ∆ ∆ ∆
∆ ∆
∆ ∆

=

θ

y

z + x
z
+
x

y

z – +
z
+

p

(a)

x

x

y

z – +
z
+

p

(b)

y

x

y

z + –
z
+

p

(c)

z

x

− y y y z z z + – – + + – x x
y
y
y
z
z
z
+
+
+
x
x
x
+
+
+

d

(a)

xy

y

d

(b)

yz

y

d

(c)

xz

z z Negative dough nut in – + x + + x-y plane + x-y
z
z
Negative
dough nut in
+
x
+
+
x-y plane
+
x-y plane
2
2
d z 2
p x –y
(d)
(e)

x

1s r 0 1 2 Å Probability
1s
r 0
1
2
Å
Probability
2s 0 r 1 2 r 2 468 Å Probability
2s
0
r 1
2
r 2
468
Å
Probability
Distance r Distance r (a) (b) 3s 2p 0 2468 Å 0 2 4 6
Distance r
Distance r
(a)
(b)
3s
2p
0
2468
Å
0
2
4
6
8
10
12
Å
Distance r
Distance r
(c)
(d)
Probability
Probability
3p Probability
3p
Probability

Distance r

(e)

3d Probability
3d
Probability

Distance r

(f)

ψ ψ

+ Na Cl
+
Na
Cl
Na + Cl –
Na +
Cl –

× ×

× ×

× ×

× ×

×

× ×

×

× ×

×

×

× ×

× ×

×

× × ×

× ×

× ×

× ×

×

×

×

×

× ×

×

×

×

×

× ×

× ×

× Br × . Br × × × × Ca: + Ca ++ (CaBr )
×
Br ×
.
Br ×
×
×
×
Ca:
+
Ca ++
(CaBr )
.
2
×
× Br ×
× Br
×
×
++
+
=
+
−−
+
=
++
+
=
µ
×
×
× ×
×
× ×
×
×
×
× ×
×
× ×
×

× × Cl × +

×

×

Cl ×

+ ×Cl

×

×

Cl

+

.

C

.

+

× Cl

×

×

.

×

×

×

.

+ ×Cl

×

×

× Cl + . C . + × Cl × × . × × × .

×

×

Cl

Cl

× ×

× ×

Cl

× ×

× ×

Chlorine

molecule

.

× × Cl × C ×Cl

.

.

.

Cl

× ×

× ×

×

×

× Carbon tetrachloride

×

molecule

 

 

H

H . . N × . × × . .
H
.
.
N
×
.
×
×
.
.

H

+

H

H

. O × . × . .
.
O
×
.
×
.
.

H

+

H

F . . B × . × × . .
F
.
.
B
×
.
×
×
.
.
 

F

F

.

.

F

+ H . . . + (NH ) H N . H × . 4
+
H
.
.
.
+
(NH )
H
N
.
H
×
.
4
H
Ammonium ion
+
.
.
+
(H
H
O
.
H
O
)
×
.
3
H
Hydronium ion
F
.
.
(BF )
F
B
F
×
.
4
F
×
×
×
×
×
.
.

           

         

−−

δ

H

+–

– F

H

+

– F

hydrogen bond
hydrogen bond

H

+

– F

H

+–

– F

H O H O H O H O Covalent H H H H bond Hydrogen
H O
H
O
H
O
H
O
Covalent
H
H
H H
bond
Hydrogen

bond

+ – + – H O ON O H O ON O + – +
+
+
H
O
ON
O
H
O
ON
O
+
+
ONO
H—O
ONO
H—O

OO + O H C HH O N H O O Salicylaldehyde o -Nitrophenol
OO
+
O
H
C
HH
O
N
H
O
O
Salicylaldehyde
o -Nitrophenol

H O H O R
H O
H O
R

H

µµµµµ

d e + e –
d
e +
e –

∴µ⇒

µ + µ + µµ α
µ
+
µ
+
µµ
α

µ µ

α

+ →

+

Q = –98.2 kcal 1 NaCl(s) Na(s) + 2 Cl (g) 2 Crystal 1 D
Q = –98.2 kcal
1
NaCl(s)
Na(s)
+
2 Cl (g)
2
Crystal
1
D = +28.9 kcal
S = +26.0 kcal
2
Determination of electron
affinity of Na atom.
Na(g)
Cl(g)
I = +118.0 kcal
(– e)
Lattice energy of
E
= ? (+e)
U 0
NaCl
crystal.
+
Na (a)
Cl
(g)
U
=
–180.4 kcal
0

→

σ

H H H : H
H
H
H
:
H

⇒ ⇒ H + H F F
H
+
H
F
F

1s

H 1s N 2p z 1s 2p y 2p x + + + + +
H
1s
N
2p z
1s
2p y
2p x
+
+
+
+
+
+

z

z y – – – NH molecule 3 + + + + + +
z
y
NH molecule
3
+
+
+
+
+
+

z

x

y y – – – NH molecule 3 + + + + + + z ′ x

z

x + + + + + 1s – – H O molecule 2
x
+
+
+ +
+ 1s
H O molecule
2

y

z

σ

p y p y p z p z p x + F atom F atom
p y
p y
p z
p z
p x
+
F atom
F atom

p x

F molecule 2
F molecule
2

σ π

p y p y p z p z p x
p y
p y
p z
p z
p x
p y p y p z p z
p y
p y
p z
p z

σ π

σ π p y p y p z p z p x p y p y

-bond

-bond

π

1s 2s 2p
1s
2s
2p

+ + + s p x p y p z sp 3 109° 28 sp
+
+
+
s
p x
p y
p z
sp 3
109° 28
sp 3
sp 3
C
sp 3
+ ++ sp 3 sp 3 sp 3 sp 3
+
++
sp 3
sp 3
sp 3
sp 3

hybrid orbitals

H C H H H
H
C
H
H
H

C

in the ground state

C

in the excited state

One 2

p hybridize to give

s

and two 2

electrons

1 s 2 s 2 p Four unpaired electrons 2 sp hybridization 2 p
1 s
2 s
2 p
Four unpaired
electrons
2
sp
hybridization
2
p

s 2 p Four unpaired electrons 2 sp hybridization 2 p -bond H H C C

-bond

H H C C -bond H H -bond
H
H
C
C
-bond
H
H
-bond

π

π

F

F 2 sp –p ( –bond) 2 sp –p ( -bond) B 2 F sp
F
2
sp –p ( –bond)
2
sp –p ( -bond)
B
2
F
sp –p ( -bond)

C

in the ground state

C

in the excited state

Electronic configuration

of sp hybridized C-atom

1s 2s 2p p x p y p z Four unpaired electrons sp hybridization 2p
1s
2s
2p
p x p y p z
Four unpaired
electrons
sp hybridization
2p

σ π σ π

H H HC
H
H
HC

CH

Be in ground state

Be in excited state

sp hybridized Be atom

2s 2p Two unpaired electrons sp hybridization with two unpaired electrons. 2p
2s
2p
Two unpaired
electrons
sp hybridization with two
unpaired electrons.
2p

sp hybridized orbitals

F Be F
F
Be
F
180° F F Be
180°
F
F
Be

σ

π

• π σ π

p x s p y p z dz 2
p x
s
p y
p z
dz 2

p x s p y p z dz 2 dsp 3 P-atom in ground state P-atom

dsp 3

P-atom in ground state

P-atom in the excited state

3s 3p 3d Five unpaired electrons 3 sp d hybridization 3d
3s
3p
3d
Five unpaired
electrons
3
sp d hybridization
3d

Cl

Cl Cl PP Cl
Cl
Cl
PP
Cl

Cl

S-atom in ground state

S-atom in excited state

3s 3p 3d Six unpaired electrons 2 sp 3 d hybridization
3s
3p
3d
Six unpaired
electrons
2
sp 3 d hybridization

F FF FF SS FF FF
F
FF
FF
SS
FF
FF

F