CHNG III

LIN KT HA HC V
CU TO PHN T
CHEMICAL
BONDING

BN CHT CA LIN KT

Electron ho tr - ns(s), ns np(p) , (n-1)d ns(d),
(n-2)f (n-1)d ns(f)

Lin kt ho hc c bn cht in (lc ht)
MT S C TRNG LIN KT
di lin kt

Gc ha tr
Bc lin kt
Nng lng lin kt
ng cong th nng
NG CONG TH NNG CA H
2


Khong cch
gia hai nhn
Th
nng
y (+)
Ht (-)
0
Hnh thnh lin kt
DI LIN KT

L khong cch gia hai ht nhn cu hai
nguyn t to lin kt.
di
lin kt
ca H
2
l
74pm
NNG LNG LIN KT
H
2
(k) H(k) + H(k) H= E
lk
= 436kJ/mol
Nng lng
lin kt

BC LIN KT

L s lin kt to thnh gia hai nguyn
t tham gia lin kt.
Acrylonitrile
Lin kt n
Lin kt i
Lin kt ba
Lin kt d
lk
(pm) E
lk
(kJ/mol)

C - C 154 346
C = C 134 610
C C 120 835
N - N 145 163
N = N 123 418
N N 110 945
Bc lin kt cng ln th lin kt cng bn
v chiu di lin kt cng ngn.
GC HA TR
(AB
n
n2 )


CC LOI LIN KT

Lin kt cng ho tr theo c hc lng t
Lin kt ion
Lin kt kim loi
Lin kt hydro
Lin kt Vanderwaals
Atomic Orbitals Molecules
LIN KT CNG HA TR
THEO C HC LNG T
1.VALENCE BOND THEORY
Linus Pauling


PHNG PHP LIN KT HA TR
(PHNG PHP VB)

Mang ngha nh tnh
2.MOLECULAR ORBITAL THEORY
Robert Mullikan (1896-1986)

PHNG PHP ORBITAL PHN T
(PHNG PHP MO)

Mang ngha nh lng
PHNG PHP LIN KT HA TR (VB)
*Quan nim v lin kt cng ha tr theo VB
*Cc loi lin kt cng ha tr v bc lin kt
*Cc tnh cht ca lin kt cng ha tr
1 2
a b
Phng trnh sng Schrodinger:

Hm sng m t chuyn ng
ng thi cu hai electron

Bi ton phn t H
2

( ) 0 V E
h
m 8
z y x
2
2
2
2
2
2
2
2
= +
t
+
c
+ c
+
c
+ c
+
c
+ c
E
0

s

r
ab



+ + +
TO LIN KT
ng cong th nng theo l thuyt VB
r
ab


Lun im c bn cu thuyt VB
Lk cht c s trn cp e (pp cp e nh ch - lk 2e 2tm)
Lk cht c hnh thnh do s che ph ca cc AO ha tr
(che ph dng )


LUN iM C BN CA PP- VB

iu kin to lin kt cng ha tr bn:

Cc AO c nng lng xp x nhau
Cc AO c mt e ln
Cc AO c cng tnh nh hng
Lin kt cng bn khi mt che ph ca cc
AO cng ln
Biu din lk cht nh sau H : H hoc H H
1.C CH GHP I : +
Kh nng to lk c quyt nh bi s AO
ha tr cha e c thn
Ch : s e c thn c th tng ln nh kch thch
Nguyn t C C
*
S di chuyn in t trong qu trnh kch thch
thng xy ra trong cng mt lp.






C CH TO LIN KT CNG HA TR
2s
2
2p
2

2s
1
2p
3

C CH CHO NHN
+

Cht cho Cht nhn

Kh nng to lk c quyt nh bi s v s
AO trng c th c khi ng t trng thi kch thch
V d O: 2s
2
2p
2
2p
1
2p
1
O
*:
2s
2
2p
2
2p
2
2p
0




Kh nng to lin kt cht (theo c hai c ch)
c quyt nh bi s AO ha tr ca nguyn t:
- Cc nguyn t chu k I c 1 AO ha tr to ti a 1 lk cht
- Cc nguyn t chu k II c 4 AO ha tr to ti a 4 lk cht
- Cc nguyn t chu k III c 9 AO ha tr to ti a 9 lk cht

Lin kt cng ha tr c tnh bo ha
TNH CHT LIN KT CNG HA TR
Tnh bo ha
S lin kt CHTcc i = s AO ha tr ca nguyn t.

Tnh nh hng
Tnh c cc v khng cc
S phn cc ca lin kt cng ho tr
F F H Cl Na Cl
_
F
= _
F
_
H
< _
Cl
_
Na
<< _
Cl
Lk cht ng cc lk cht c cc Lk ion
H
o+
Cl
o-

Cl b phn cc m
H b phn cc dng

Cc loi lin kt cng ha tr v bc lin kt
Ch : cc vng xen ph phi cng du
Lin kt Sigma (o)
Cc AO che ph dc theo trc lin kt
Nhn trc lin kt lm trc i xng.
Lin kt khng lm cn tr s quay t do
cu cc nguyn t quanh trc lin kt
bn

(ns-ns) < (ns-np) < (np-np)

+
+ +
+ + + - - -
+ +
Lin kt Pi (t)
Hai AO che ph
hai pha cu trc
lin kt.
C mt phng phn
xng cha trc lin
kt.


Trc lin kt
+ +
_ _
Lin kt
Cc nguyn t thuc chu k 2 c kh nng
to lk t
2p-2p
hoc t
2p-3p


Cc nguyn t thuc chu k 3 tr i ch c
kh nng hnh thnh lin kt t
p-d
, t
d-d


S lin kt t(ghp i)= (s oxh)
nttt
s lk

Lin kt n
Lin kt n lun lun l lin kt
Lin kt bi
Trong lin kt bi th s c 1 lin kt phn cn
li s l cc lin kt t
Lin kt khng nh ch
Cp electron lin kt khng thuc hn
v mt cp nguyn t no c m phn
b ng u cho mt s ht nhn
nguyn t k cn.
B
Cl
Cl
Cl
:
: :
1/3t
1/3t
1/3t
Lin kt
Lin kt o c to thnh khi hai AOd
che ph bng tt c bn cnh.

Lin kt o thng gp trong phc cht
ca kim loi chuyn tip hoc mt s
hp cht ca cc nguyn t thuc chu
k 3.
Lin kt o ca cc AO d
Z
Y
X
Z
Z
Z
Y
Y
Y
X
X
X
BC LIN KT
BC LK = 1(lko)+s lkt
c
+s lk t
kc
/scpngt

Bc lin kt c th l s l khi c mt lin kt t
khng nh ch
LIN KT CNG HA TR CA H
2
S
V sao gc ha tr khng l 90
0
?
THUYT SC Y CP IN T HA TR
Valence Shell Electron Pair Repulsion(VSEPR )
Trong phn t cng ho tr AB
n
cc cp
in t ha tr lin kt () v cp in t
ho tr t do cu A (nu c) phi xa nhau
mc ti a sao cho lc y gia cc
cp electron c gi tr nh nht.
nh hng trong khng gian cu cc cp
e lin kt() hoc e t do quanh A
2 charge clouds,
linear
3 charge clouds,
trigonal planar
4 charge clouds,
tetrahedral
Nguyn t A phi trng thi lai ha.
S cp e quanh A s quyt nh trng thi lai ha
ca nguyn t trung tm A .


Lai ha l g ?
Nguyn t trung tm A s dng cc AO
ha tr: s,p,d,f..trong ni b nguyn t
em pha trn vi nhau to thnh cc
AO lai ha.
Cc AO lai ha ny s tham gia to lk
vi B hoc cha in t t do ca A.
c im cc AO lai ha

S cp e(td+lk)quanh A =S AO tham gia lai ho
= s AO lai ho.
AB
2
, s cp e quanh A = 2 A lai ha sp , 2AO lh sp


Phn b i xng vi nhau trong khng gian

Cc AO lai ho c mc nng lng bng nhau

Cc AO lai ha c kch thc hnh dng ging
nhau, mt electron dn v mt pha.

Cc AO lai ha cu A to lk vi B bn hn
so vi AO khng lai ha
iu kin lai ha bn
Nng lng ca cc AO tham gia lai ha xp
x nhau
Mt e ca cc AO tham gia lai ha ln
Mc che ph cu cc AO phi cao





Trong mt chu k: AE
ns - np
nn kh nng Lai Ha


Li Be B C N O F Ne
AE
2p 2s
1,9 2,8 5,7 8,1 11,4 18,9 22,6 26,8
Trong mt phn nhm chnh: r kh nng LH
S cp e quanh A = s cp e
td
+ s cp e
lk
= 2 A:sp lai ha thng
= 3 A:sp
2
lai ha tam gic


= 4 A:sp
3
lai ha t din



S cp e quanh A= 1/2{ (e
ht
)AB
n
-8(2)n}+n
n 2 A khng l cc kl chuyn tip
V d: BeCl
2
- s cp e quanh Be = (16-8.2) +2=2
Besp
Lai ha sp
S cp e quanh A= 2 A trng thi lai ha SP
AB
2
dng thng gc lk 180
0

linear
LAI HO SP
A * 2s
1
2p
1

Lai ha sp

BeCl
2
(AB
2
E
0
) BLK=1; 180
0

s cp e quanh Be= (16 8.2)+2=0+2=2sp

Be: 2s
2
2p
0





|+

Be
*
2s
1
2p
1

Lai ho sp
+
+
|+
|+
|+ |+
o
o
o o
Hai AO lai ha ca Be
Cl: 3s
2
3p
5

Cl: 3s
2
3p
5

sp

Lai ha sp
2

S cp e quanh A= 3 A trng thi lai ha SP
2

AB
3
E
0
,AB
2
E
1
- gc ha tr 120
0
trigonal planar
LAI HA SP
2

Lai ha sp
2

BCl
3
(AB
3
E
0
) BLK = 1,33 ; 120
0

s cp e quanh B= (24-8.3)+3=0+3=3sp
2

B: 2s
2
2p
1


Cl
Cl
Cl
3p
|+ |+ +
|+ + |+
|+ |+ +
|
|+
Cl : 3s
2
3p
5

Cl : 3s
2
3p
5


Cl : 3s
2
3p
5


B
*
: 2s
1
2p
2

|
|
| | |
o
o
o
Ba AO lai ha sp
2
ca B
sp
2

o
o
o
Lai ha sp
3

S cp e quanh A= 4 A trng thi lai ha SP
3

AB
4
E
0
, AB
3
E
1
, AB
2
E
2
- gc ha tr 109
0
28

tetrahedral
LAI HA SP
3

CH
4
(AB
4
) blk=1 ; 109
0
5
s cp e quanh C= (8-2.4)+4=0+4=4sp
3

C : 2s
2
2p
2

+ + + +
| | | |
|+
|+
C
*
: 2s
1
2p
3

| |
H H

H H
sp
3

o o o o
|
|
NH
3
(AB
3
E
1
) blk=1 ; HNH=107
0
3
s cp e quanh N=1/2(8-2.3)+3=1+3=4sp
3

N : 2s
2
2p
3

+ + +
|+
| | |
|+ | | |
o o o
H H H
sp
3

Cp e t do
Thp tam gic
H
2
O (AB
2
E
2
) blk=1 ; HOH= 104
0
5
s cp e quanh O = (8-2.2)+2=2+2=4sp
3

O : 2s
2
2p
4

| | |+ |+
+ +
| | |+
|+
sp
3

o o
H H
Gc
2e
lk
2e
lk

Lc y
2e
td
2e
td

Lc y
2e
td
2e
lk

Lc y
> >
nh hng ca cp in t t do
n gc ha tr
2e
lk
2e
lk

Lc y
2e
td
2e
td

Lc y
2e
td
2e
lk

Lc y
> >
nh hng ca cp in t t do
Momen lng cc v phn t cht c cc
H
F
electron rich
region
electron poor
region
o+
o
Momen lng cc = o x
o : in tch [n v tnh in]
: khong cch gia hai in tch [cm]

IU KIN PHN T CNG HA TR C CC
Lin kt cng ha tr c cc
Cu ta phn t khng i xng

Momen lng cc cu phn t l tng
vect momen lng cc cu cc lin
kt v cp electron ho tr t do trong
cc AO lai ha c trong phn t.
C cc hay khng cc?
BF
3
, Cl
2
CO, v NH
3
.
Phn t khng cc,BF
3

F
F F
B
Nguyn t B
b phn cc
dng v
nguyn t Fb
phn cc m.
Lin kt BF trong pt BF
3
l
c cc.
Nhng phn t c cu to i
xng nn khng cc.
Molecular Polarity, HBF
2

B b phn cc
dng nhng
H & F b phn
cc m.
H
F F
B
Lin kt BF v BH trong
HBF
2
l c cc. Nhng do pt
khng i xng nn c cc.
Substituted
Ethylene
Lin kt CF phn cc mnh hn lin
kt CH.
Do c hai lin kt CF cng mt pha
,phn t c cc.
Substituted
Ethylene
Lin kt CF phn cc mnh hn lin
kt CH.
Do c hai lin kt CF nm hai pha
i nhau , phn t khng phn cc
Tnh cht t ca phn t
- Cht thun t (Paramagnetic): cht c
electron c thn .Cht ny khi t trong t trng
s b nam chm ht.
- Cht nghch t (Diamagnetic):cht khng c
in t c thn .Cht ny khi t trong t trng
s b y.