GV.

Trn Minh Hi

CHNG 3:

LIN KT HA HC

3.1. I CNG V LIN KT HA HC 3.1.1. Phn t v lin kt ha hc Phn t gm mt s gii hn cc ht nhn nguyn t v cc electron tng tc vi nhau v c phn b mt cch xc nh trong khng gian to thnh mt cu trc vng bn. Hiu theo ngha rng, phn t khng ch bao gm nhng phn t trung ha nh phn t H2, phn t CO2 m cn bao gm cc ion (NO3-) hay cc gc t do nh CH3 Thc t cho thy, tr cc kh him, cc nguyn t ca nhng nguyn t khc c khuynh hng kt hp vi nhau (H2, NaCl, HCl). Hai nh khoa hc Gilbert N. Lewis v W. Kossel cho rng s d nh vy l v khi lin kt vi nhau, cc nguyn t c th t c cu hnh electron tng t kh him (ns2, np6) bn hn cu hnh tng nguyn t ring l. Lin kt ion theo Kossel (c). Nm 1916 nh khoa hc c W. Kossel lin h vn lin kt gia cc nguyn t vi cu hnh elecetron ca chng. ng thy rng trong mt s trng hp, phn t hp cht to thnh nh s chuyn electron ha tr t nguyn t ny sang nguyn t kia. + Gii thch: Phn t ca hp cht ha hc c to nn nh s chuyn electron ha tr t nguyn t ny sang nguyn t kia. Nguyn t mt electron bin thnh ion dng ( Gi l cation) Nguyn t thu electron bin thnh ion m (Gi l anion) Sau cc ion mang in tch ngc du ht nhau v li gn nhau, nhng khi n rt gn nhau gia nhng ion xut hin lc y sinh ra bi tng tc gia v electron ca cc ion. Lc y cng tng ln khi cc ion cng gn nhau, n lc lc y bng lc ht, cc ion dng li v cch nhau mt khong nht nh, khi lin kt ion c hnh thnh. VD: Qu trnh hnh thnh phn t NaCl + Nguyn t Na (Z=11): [Ne]3s1

+ Nguyn t Cl ( Z = 17): [Ne]3s23p5

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+ Na 1e- Na+ (Cation) + Cl + 1e- Cl(Anion)

Na Na Na+ Cl-

1eClCl

Sau khi Na mt electron bin thnh Na+ th bn knh nh i cn Cl nhn electron bin thnh Cl - th bn knh ln hn so vi trng thi nguyn t trung ha. Hai ion Na+ v Cl- ht nhau bng lc ht tnh in, chng s tip xc nhau mt khong cch bng tng bn knh ca hai ion

- Hn ch: Khng gii thch c s to thnh mt s rt ln phn t to nn bi nguyn t ca cng mt nguyn t nh Cl2, H2hoc ca nhng nguyn t gn ging nhau nh SO2, CO2 Nh vy, lin kt ion l loi lin kt nh lc ht tnh in gia cc ion tri du. Lin kt ion ch hnh thnh gia cc kim loi in hnh v cc phi kim in hnh. Ha tr ca mt nguyn t trong hp cht ion c gi l in ha tr ca nguyn t. in ha tr ca nguyn t c tnh bng s in tch ca ion . Trong trng hp v d trn, in ha tr ca Na bng +1 v ca Cl bng -1. Lin kt cng ha tr theo Lewis Nm 1916, nh khoa hc M G. Lewis cho bit trong nhiu trng hp lin kt c hnh thnh bng cch nguyn t a ra electron ha tr ca mnh to thnh mt, hai hay ba cp electron chung gia hai nguyn t. Gii thch:
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Cc nguyn t a ra nhng electron ha tr ca mnh to thnh 1,2 hay 3 cp electron chung gia hai nguyn t mi nguyn t t c cu hnh electron bn ca kh him ns2 hay ns2np6. VD:
Cl + Cl

Cng thc electron

Cl Cl

Cng thc cu to
( Cl- Cl )

N H

+ +

N Cl

N H Cl

( N N) ( H - Cl)

Nu thay mi cp electron chung bng mt vch ni ta c cng thc cu to. - C hai loi lin kt cng ha tr: * Lin kt cng ha tr khng cc: Cp electron chung gia hai nguyn to nn lin kt thuc v hai nguyn t vi mc nh nhau. VD: H2, Cl2 (H-H) * Lin kt cng ha tr c cc: Cp electron chung lch v pha nguyn t ca nguyn t c m in ln hn. VD: Trong phn t HCl th cp electron chung lch v pha Clo. Lin kt cng ha tr khng phn cc v lin kt ion l hai trng hp gii hn ca lin kt cng ha tr c cc - Hn ch: Khng gii thch c:
Cu trc ca cc phn t khng tun theo quy tc bt t nh BeCl2, BeCl3. Gc gia hai nguyn t to lin kt S hin din ca cc phn t c s electron l. VD: BeCl3

Lin kt phi tr (Lin kt cho - nhn)

- L lin kt cng ha tr nhng trong cp electron chung do mt nguyn t ng gp ( thng dng mi tn ch lin kt cho - nhn) VD:

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+ H

H H N H + H+ H

H N H +

(NH4+)
+

H O H

H+

H O H H

hay

H O H H

(H3O+)

in tch dng tr thnh in tch chung ca c ion H 3O+ v ca c ion NH4+ ch khng thuc nguyn t Hyro no c

snh hai loi lin kt So

Lin kt ion - Lin kt bng lc ht tnh in - Thng lin kt ion hnh thnh gia hai nguyn t ca nguyn c m in khc nhau nhiu. VD: Gia kim loi in hnh v phi kim in hnh nh NaCl - C nhit nng chy v nhit si cao - Khng c hng Lin kt cng ha tr - Lin kt bng cp electron chung - Lin kt thng hnh thnh gia hai nguyn t ca nguyn t c m in ging hoc khc nhau khng nhiu. VD: H2, HCl - C nhit nng chy v nhit si thp. - C hng

3.3. Phng php lin kt ha tr (VB) (Valence bond)

Thuyt tnh in ca Ctxen cng nh thuyt cp electron ca Liuyt u cha gii thch r v y v bn ca lin kt v hnh hc ca phn t. Hai thuyt gn ng c s dng rng ri gii thch bn cht ca lin kt cng ha tr ni ring hay ca lin kt ha hc ni chung l thuyt lin kt ha tr ( vit tt l thuyt VB) v thuyt oribitan phn t ( vit tt l thuyt MO). 3.3.1. Mt s lun im c bn Thuyt VB xut pht t nhng lun im sau: Lun im 1: Lin kt hnh thnh l do s kt i ca hai electron spin tri du. y s c s xen ph ca hai orbitan nguyn t ca hai nguyn t, mi orbitan mang mt electron. Vy khi to thnh phn t cc nguyn t vn gi nguyn kin trc electron.
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VD: Khi hai nguyn t Hyro c cha electron spin tri du tin gn n nhau th chng ht nhau lm nng lng ca h gim xung th h tr thnh vng bn. Lc ny lin kt ha hc xut hin do hai electron spin ngc du c th chuyn ng gn c hai ht nhn, ni cch khc l hai electron ny tr thnh chung cho c hai ht nhn nguyn t Hyro

Lin kt cng ha tr c gi l lin kt hai electron hai tm. Lun im 2: iu kin to lin kt ha hc gia hai nguyn t l chng c nhng electron c thn c th ghp i c. VD: Li : 1s22s1 V c 1 electron c thn nn Li c th to c 1 lin kt

2s
C: 1s22s22p2

2p

Sau khi nhn nng lng th C trng thi kch thch

2s

2p

C*1s22s12p3
V c 4 electron c thn nn Cacbon c th to c 4 lin kt
2s 2p

O: 1s 2s 2p
2 2

V c 2 electron c thn nn O to c 2 lin kt. Lun im 3:

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Mc xen ph ca cc orbitan cng ln th lin kt cng ha tr cng bn. Mc ny ph thuc vo cc yu t sau: + Kch thc, hnh dng orbitan (s, p, d, f) + Hng xen ph theo trc hay song song + Kiu xen ph 3.3.2. Tnh c hng ca lin kt cng ha tr. Mi lin kt cng ha tr trong phn t c phn b theo nhng phng sao cho s xen ph ca cc orbitan nguyn t l ln nht. VD1: Gii thch phn t PH3 theo thuyt VB B1: Vit cu trc electron ca cc nguyn t P(Z=15): [Ne]3s23p3

H(Z=1): 1s1

B2: Cc orbitan cha electron c thn s ln lt xen ph vi nhau to thnh lin kt Mi orbitan p ca P s lin kt vi mt orbitan 1s ca H To thnh kt P-H
HPH = 900 (gc l thuyt theo VB) Gc HPH = 930(gc thc nghim) Thc t gc
z

3 lin

H H H
y x

Gc thc nghim ln hn gc l thuyt 30, l do s y nhau ca cc nguyn t H v ca cc i electron tham gia lin kt.

VD2: Gii thch cu trc phn t H2S theo thuyt VB S (Z=16) [Ne]3s23p4
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z

H (Z=1) 1s1 To thnh hai lin kt S-H

H
y

Theo thuyt VB, nguyn t H s tin ti nguyn t S theo 2 phng ca Sx v Sy, c s che ph cc i gia orbitan s ca nguyn t H v orbitan px, py ( chng hn) ca nguyn t S. Theo thuyt VB:
HSH Thc t gc

= 900 nhng thc t gcHSH = 920

*u - Khuyt im ca thuyt VB: Thuyt VB c th gii thch c gc ca lin kt, tuy nhin so vi thc t th gc ny cn cha ph hp. Thuyt ny dng s y nhau gia i electron lin kt v nguyn t lin kt vi nguyn t trung tm. Tuy nhin cn nhiu trng hp th so vi thc t cn lch qu xa. i vi cc phn t hp cht ca C, Sith vn cn kh khn hn na. VD: Gii thch cu trc phn t CH4 theo thuyt VB C (Z= 6) 1s22s22p2 H (Z= 1) 1s1 C*: 1s22s12p3 4 orbitan ny s lin kt vi 4 orbitan s ca H to thnh 4 lin kt C-H

HCH

Theo thuyt VB th 3 lin kt C-H c gc

= 900
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V 1 lin kt C-H do s xen ph ca orbitan 1s ca nguyn t H vi orbitan 2s ca nguyn t C, nn v tr ca n khng xc nh c.

HCH Thc t gc

= 109028v 4 lin kt C-H u ging nhau. Ngha l phn t CH4 c cu trc khng

gian ca t din u, C tm cn 4 nguyn t s 4 nh ca t din. khc phc iu ny, Pauling a ra thuyt lai ha gii thch c cu phn t ca cc trng hp c bit ny. 3.4. Thuyt lai ha cc orbitan nguyn t (S dng electron c thn) - Theo Pauling, khi to thnh lin kt, cc electron ha tr ca nguyn t khng tham gia mt cch ring r m cc orbitan ca chng s trn ln nhau hay ni mt cch ton hc, chng s t hp vi nhau thnh nhng t hp tt nht to thnh cc lin kt bn hn. S t hp cho ta nhng orbitan lai ha tng ng nhau. VD:
CH4 C*

Cc orbitan khng tham gia ring r nh vy M

C*

Cc orbitan lai ha hon ton ging nhau

c im ca cc orbitan lai ha:

+ Hnh dng ging nhau, nng lng ging nhau + Khc nhau v v tr trong khng gian - S lai ha ch xy ra mt nguyn t trong phn t, l nguyn t trung tm

Cc kiu lai ha
* Lai ha sp
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C s t hp ca 1 orbitan s vi 1 orbitan p to thnh 2 orbitan lai ha sp (

1800

spa

spb

Dng gii thch c cu trc ca cc phn t sau y : CdX2, BeX2, ZnX2, HgX2 vi X l Halogen v C2H2 VD : Gii thch cu trc phn t BeCl2
2s 2p

Be (Z=4) : 1s22s2
Be*

1 orbitan s + 1 orbitan p to thnh 2 orbitan lai ha sp. Mi orbitan lai ha mang 1e- c thn. Cl (Z = 17) : [Ne]3s23p5

Hai orbitan lai ha sp, mi orbitan mang 1 electron c thn che ph vi 2 orbitan p ca 2 nguyn t Clo ( Mi orbitan p mang mt electron c thn) to thnh hai lin kt: Be-Cl

Cl

Be

Cl

Cl

Be Cl

Phn t BeCl2 c cu trc thng, gc lin kt = 1800 * Lai ha sp2 1 orbitan s t hp vi 2 orbitan p to thnh 3 orbitan lai ha sp2
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z

1200

Dng gii thch c cu trc ca phn t: BX3 vi X l cc Halogen v C2H4 VD: Gii thch cu trc phn t BCl3
2s 2p

B(Z=5): 1s22s22p1
B*
Cl

Cl

Cl

B
Cl

Cl

Dng 1 orbitan s t hp vi 2 orbitan p to thnh orbitan lai ha sp2. Mi orbitan mang mt

Cl

electron c thn s che ph vi 3 orbitan p ca 3 nguyn t Cl to thnh 3 lin kt B-Cl * Lai ha sp3 1 orbitan s t hp vi 3 orbitan p to thnh 4 orbitan lai ha sp3

Dng gii thch c cu trc ca cc hp cht MX4 vi X l cc Halogen M: C, Si nh CH4, SiCl4 VD : Gii thch cu trc phn t CH4 theo thuyt lai ha C (Z = 6) 1s22s22p2
2s 2p

C*

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1 orbitan s t hp vi 3 orbitan p to thnh 4 orbitan lai ha sp3. H (Z= 1) 1s1 Mi orbitan lai ha sp3 mang 1 electron c thn s che ph vi nguyn t H to thnh 4 lin kt C-H Phn t CH4 c cu trc t din u, gc lin kt l: 109028 orbitan 1s ca

So snh thuyt VB v thuyt lai ha:

Thuyt VB Thuyt lai ha Ging nhau: S dng electron c thn to thnh lin kt Trc khi to thnh lin kt cc orbitan Khng c s lai ha ca cc orbitan cha electron c thn tin hnh lai ha vi nhau

3.5. Cc kiu xen ph Orbitan nguyn t

* Lin kt

- Hnh thnh do s xen ph ca 2 orbitan dc theo trc lin kt ni 2 tm nguyn t. - S xen ph mc cao nn lin kt to ra kh bn vng.
s s

- Cc orbitan lai ha cng c kh nng to thnh lin kt

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Lin kt

- Hnh thnh do s xen ph bn ca 2 orbitan - Xy ra khi c s xen ph: p-p, p-d, d-d - Ch xy ra gia 2 orbitan thun khit ( cha tham gia lai ha) - C mt phng i xng - Km bn hn lin kt

p-p

p-d

d-d

Ch : + Lin kt n gm 1 lin kt

H H
+ Lin

H2C CH2

kt i gm 1 lin kt

v 1 lin kt

+ Lin kt ba gm 1 lin kt

v 2 lin kt

HC CH

3.8. Vi nt c trng ca lin kt

3.8.1. di lin kt v gc ha tr
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* di lin kt (n v
A
0

- L khong cch gia hai ht nhn nguyn t trong lin kt - Trong nhng hp cht khc nhau, di ca cng mt lin kt thng bin i khng ng k VD: O-H (H2O)= 0,96 O-H (CH3OH) = 0,96

- di lin kt gia hai nguyn t gim xung khi bi ca lin kt tng ln VD: di lin kt C-C H3C-CH3 1,54
H2C CH2
HC CH

A
thnh bi hai on thng nguyn t lin kt. VD
H

* Gc ha 1,34 1,2 tr L gc to

O 104,50 H

tng tng ni ht nhn nguyn t trung tm vi hai ht nhn :

3.8.2. Nng lng lin kt (n v KCal/mol hay KJ/mol) a/ Khi nim - L nng lng cn tiu tn ph v (lm t lin kt) b/ Cch tnh + Phn t A2:
Li2 Br2 Li + Li Br + Br

H = +25 Kcal/mol H = +192

+ Phn t AB:
H Cl H + Cl

H = +103

+ Phn t ABn: * Ta c gi tr nng lng trung bnh * C 2 cch tnh:

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Cch 1: Nng lng lin kt trung bnh =

1 n

Nng lng ca cc lin kt

VD:
H3 C H2 C HC C H H H H H = +102 H = +87 Kcal/mol H = +125 H = +81 Kcal/mol

Nng lng lin kt trung bnh C-H: HC-H =

(102 + 87 + 125 + 81) = 98,7 Kcal/mol

1 4

Cch 2: Nng lng lin kt trung bnh =

1 n

Nng lng to thnh phn t t cc nguyn t trng

thi kh (ly gi tr tuyt i) VD: Nng lng to thnh ca qu trnh C + 4H CH4 l - 394,8 Kcal/mol Nng lng trung bnh ca mi lin kt C-H trong CH4 l
1 4

.394,8 = +98,7 (Kcal/mol)

CH (Nng lng to thnh lin kt (< 0) v nng lng ph v lin kt (> 0) c gi tr bng nhau nhng ngc du) c/ Tnh cht - Lin kt cng bn th nng lng lin kt cng ln ( l thc o bn lin kt) - Nng lng lin kt tng khi bi ca lin kt tng
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VD :

H(
C C

) = 145,8 Kcal/mol ) = 199,6(Kcal/mol)

C C

H(

3.8.3. phn cc ca lin kt - phn cc ca phn t * phn cc ca lin kt Khi hai nguyn t A,B c m in khc nhau lin kt vi nhau cho lin kt cng ha tr phn cc th cp electron chung s lch v pha nguyn t c m in ln hn (gi s A) th pha A c d in tch m v pha B c d in tch dng ngha l hai u ca phn t tch in bng nhau nhng ngc du nhau ( A- - B+). Khi xut hin mt mmen lng cc vi
= qd

( thng hng t dng sang m) q : l gi tr tuyt i ca in tch q ca mi tm in tch d: l khong cch gia tm ca in tch dng v tm ca in tch m n v ca momen lng cc l Debye (D) * phn cc ca phn t Trong phn t a nguyn t, phn cc phn t c tnh bng tng vect phn cc lin kt.

tng = 0 Tm in tch dng trng vi tm in tch m. Phn t khng c cc.

VD:
O C + Oq- 2q q

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tng 0 Tm in tch dng khc tm in tch m. Phn t c cc. VD:

=
O H

= 1,58D

= 1,84D

*Gi tr ca momen c xc nh bng thc nghim

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