Kho st mt s dn xut halogen, ancol,

phenol v axit cacboxylic bng phng php

ha hc lng t


Nguyn H My


Trng i hc Khoa hc T nhin
Lun vn ThS. ngnh: Ha l v ha l thuyt; M s: 60 44 31
Ngi hng dn: PGS.TS. Phm Vn Nhiu ; TS. Nguyn Ha Mi
Nm bo v: 2012


Abstract. Nghin cu c s l thuyt ha hc lng t, phng trnh Schrodinger,
s gn ng Born Oppenheirmer (Bon-Openhem, phng php bin phn, thuyt
trng t hp Hartree-Fork, phng trnh Roothaan. Nghin cu c s ca cc
phng php tnh gn ng lng t, c s l thuyt ha hc hu c. Dn xut
halogen, Anco, Phenol, Axit cacboxylic.

Keywords. Ha l; Ha hc lng t


Content
M U
Ha hc lng t bt u pht trin t khong nhng nm 30 ca th k XX v ngy
cng chng t l mt l thuyt khng th thiu trong mi lnh vc ha hc. Ha hc lng t
l ngnh khoa hc nghin cu cc h lng t da vo phng trnh chnh tc ca c hc
lng t do Schorodinger a ra nm 1926, v nhanh chng tr thnh cng c hu ch ca
ha l thuyt i su tm hiu, nghin cu vn ct li nht ca ha hc l cu trc v cc
tnh cht ha l ca cc cht.
Cc quy lut phn ng th vo mt s hp cht hu c, c bit l phn ng th vo
vng benzen l nhng quy lut thc nghim c hnh thnh rt lu, v c s dng nhiu
trong ging dy ha hc hu c. Cc nghin cu khoa hc ch ra c hng th vo lin
kt C H trong vng benzen. Tuy nhin cho n nay cha c ti liu no cng b s liu gii
thch v lm r thm nhng quy lut trn. GAUSSIAN l phn mm pht trin vt tri v
cc phng php ab initio (DFT) kh hiu qu, c nhiu nh nghin cu chuyn nghip s
dng. Vi cc thut ton c vit tt hn, cc bc ti u ha ca Gaussian cn 4 chun hi
t trong khi Hyperchem ch c 1. Tuy chy hi chm nhng c chnh xc kh cao, v th
y l mt cng c hu hiu tr gip cc nh ha hc thc nghim trong nghin cu ca
mnh.
T nhng l do trn, chng ti chn ti nghin cu :Kho st mt s dn xut
halogen, ancol, phenol v axit cacboxylic bng phng php ha hc lng t.
Lun vn gm cc phn m u, ni dung, kt lun, ti liu tham kho v ph lc.
Phn ni dung chnh gm 3 chng.
Chng 1. Tng quan
Chng 2. i tng v phng php nghin cu
Chng 3. Kt qu v tho lun
Chng ti hy vng cc kt qu ca lun vn c th gp phn lm r hn hng mt s phn
ng v l ti liu tham kho cho vic ging dy ha hc trng ph thng.


CHNG 1: TNG QUAN

1.1. C S L THUYT HA HC LNG T
1.1.1. Phng trnh Schrodinger
S bin i trng thi vi m theo thi gian ca h lng t c m t bi phng trnh
Schrodinger (Sroding, 1926) c dng tng qut:
i
t
c
=
c
(1.1)
( , ) q t + Hm sng m t trng thi ca h lng t. l hm ca ta (q) v thi gian t.
2
2
2
H T U U
m
. .
= + = V +

Vi
2 2 2
2
2 2 2
x y z
c c c
V = + +
c c c
: ton t Laplace
U: th nng (nng lng tng tc gia cc ht lng t trong h)
Trong trng hp th nng ca h khng ph thuc vo thi gian:
U = U(q) (q: ta )
H kn, hoc h chuyn ng trong mt trng ngoi khng i, th ton t Hamilton
H
.
khng ph thuc vo thi gian v trng vi ton t nng lng ton phn H
.
(q), cn trng
thi ca h c gi l trng thi dng: ( , ) ( ) q t q . Khi phng trnh Schrodinger
c vit di dng:
( ) ( ) ( ) H q q E q
.
= (1.2)
y E l tr ring nng lng, ( ) q l hm sng (q: ta tng qut (x, y, z)
hay (r, , u ). Khi nghim ca phng trnh (1.1) c th vit di dng:
( , ) ( ).
iET
q t q e

=

(1.3)
Nhng trng thi (1.3), h lng t c gi tr xc nh gi l nhng trng thi dng v
phng trnh Schrodinger (1.2) l phng trnh Schrodinger cho nhng trng thi dng, c
dng trong ha lng t.
1.1.2. Phng php bin phn
Mc ch ca phng php da trn MO LCAO l tm ra c
ij
gn ng nht vi hm
sng thc t ng vi nng lng cc tiu theo tp hm c s chn. Bin i t phng
trnh Schrodinger ta c:
*
*
H d
E
d
t
t
=
}
(1.8)
y dt l th tch v cng nh ca khng gian v spin.
Nu hm chun ha th tch phn mu bng n v v phng trnh c dng:
*
E H d t =
}
(1.9)
Khi p dng phng php bin phn, hm sng gn ng thng c biu din
di dng MO LCAO trn, tc l:
1 1 2 2 3 3
....
n n
c c c c = + + + + (1.10)
1.1.3. Thuyt trng t hp Hartree-Fock
Phng php gn ng u tin c s dng gii phng trnh (1.2) l phng
php gn ng Hartree Fock (HF). T quan im vt l v trng th hiu dng trung bnh
ha i vi mi electron hp bi th ht ca ht nhn v th y trung bnh ha do tt c cc
electron khc sinh ra.
1.1.4. Phng trnh Roothaan
Phng php Hartree Fock cp trn thun tin i vi vic s dng trong nhng
trng hp trng Coulomb i xng cu, tc l i vi cc nguyn t. Tuy nhin, n kh
tnh c i vi nhng phn t, khng c trng Coulomb i xng cu. Roothaan (1951)
s dng cc tp hm c s m rng phn khng gian (bn knh) ca cc hm spin
orbitan. Vic ny gip chuyn cc phng trnh HF thnh mt bi ton ma trn c th gii
c.
1.2. C S CA CC PHNG PHP TNH GN NG LNG T
Cc phng php tnh gn ng c xy dng trn c s phng trnh Roothaan.
Hu ht cc phng php ny u tp trung gii quyt vn th nng tng tc gia cc
electron vi nhau da vo vic gii gn ng cc phng trnh cha tch phn Coulomb v
cc tch phn xen ph gia cc electron.
Vi mt lng ln cc electron cc tch phn a tm xut hin trong cc s hng J, K
(trong phng trnh 1.19) hu nh khng th gii c. khc phc nhng tr ngi ,
ngi ta s dng mt s phng php bn kinh nghim khc nhau da vo mt s gi thit
gn ng sau:
- Gim b hm c s.
- B qua mt s tch phn.
- Thay th mt s tch phn bng cc hm n gin c cha tham s rt ra t thc
nghim. Nhng tham s c c bng cch o hay tnh ton nh th ion ha, i lc
electron, ph,...
- Xem xt cc h thng cc electron o v cc electron t ring r.
Cc phng php tnh gn ng hin nay bao gm cc phng php tnh khng kinh nghim
Ab initio (tnh ton cc tham s trn m hnh c lng) v cc phng php bn kinh
nghim s dng cc tham s thc nghim: CNDO, NDDO, AM1, PM3, MINDO, ZINDO...
1.3. C S L THUYT HA HC HU C
Electron l tiu phn linh ng nht trong phn t, d cha tham gia lin kt hoc
tham gia lin kt n u c th b dch chuyn bi nh hng tng h ca cc nguyn t
trong phn t.
Thuyt dch chuyn electron xut hin t nm 1920, trc thi k pht trin ca
thuyt obitan phn t. n gin v d hiu, n gip gii thch a s cc d liu thc
nghim c lin quan n cu trc, tnh cht v kh nng phn ng ca cc hp cht hu c, v
vy n c p dng rng ri cho n nay.
1.3.1. Hiu ng cm ng.
- Bn cht: hiu ng cm ng l s phn cc cc lin kt, lan truyn theo mch cc lin kt
o do s khc nhau v m in.
- Phn loi:
+I I=0 -I
Y C C H C X
o o o o + +


Y l nhm y electron gy nn hiu ng cm ng dng (+I) nh cc nhm mang in tch
m: -S
-
, O
-
, cc gc ankyl C
n
H
2n+1
-
....
X l nhm ht electron gy nn hiu ng cm ng m (-I) nh cc ht mang in tch dng:
-N
+
R
3
; cc nguyn t c m in ln nh: - F, -Cl, -OR, -SR, -NR
2
...; cc gc hirocacbon
khng no: CH
2
=CH-; C
6
H
5
-....
Nguyn t H coi nh khng c s ht hay y electron.
- c im: hiu ng cm ng gim rt nhanh khi ko di mch truyn nh hng. Hiu ng
cm ng khng b cn tr bi cc yu t khng gian.
1.3.2. Hiu ng lin hp
- Bn cht: Hiu ng lin hp l s phn cc cc lin kt lan truyn trong h lin hp (biu
th bng mi tn cong).
- Phn loi:



Hiu ng +C C = 0 -C
1.3.3. Hiu ng siu lin hp:
- Hiu ng siu lin hp dng l hiu ng y electron do tng tc gia cc eletron cc lin
kt C H
o
v electron p ca ni i hay vng benzen. K hiu +H ( t ting anh
Hyperconjugation). Hiu ng +H tng khi s lin kt C H
o
tng.
-CH
3
> - CH
2
CH
3
> - CH(CH
3
)
2
> - C(CH
3
)
3
(Ngc vi hiu ng cm ng)

- Hiu ng siu lin hp m
Nhm C H
o
lin kt vi h thng lin kt p c th gy nn hiu ng siu lin hp ht
electron gi l hiu ng siu lin hp m (-H).
1.3.4. Hiu ng khng gian
Loi hiu ng do kch thc ca nhm nguyn t gy nn c gi l hiu ng khng gian,
k hiu l S ( t ting anh Steric Effect).
1.3.5. Hiu ng ortho
Cc nhm th v tr ortho trong vng benzen thng gy nhng nh hng rt bt
ng n tnh vt l cng nh tnh cht ha hc ca phn t.
Chng hn cc axit ng phn ortho RC
6
H
4
NH
2
c hng s pK
b
ln hn cc ng phn khc
bt k bn cht ca nhm th l g. Loi nh hng c bit ca nhm th v tr ortho nh
vy gi l hiu ng ortho.
Hiu ng ortho khng n thun l hiu ng khng gian m l mt hiu ng hn hp ca
nhiu yu t.
- Hiu ng khng gian loi 1: Nhm X v tr ortho cn tr s tn cng ca tc nhn Y vo
nhm chc Z.
- Hiu ng khng gian loi 2: Nhm X lm mt tnh ng phng ca h.
- Hiu ng cm ng: Nhm X c v tr ortho gn nhm chc hn nn th hin mnh hn
cc v tr khc, ngoi ra cn c tc dng trc tip nh hiu ng trng.
- To lin kt hidro ni phn t.
1.3.6. Phn ng th nhn thm
Vng thm kiu benzen l vng lin hp kn rt bn vng v c nng lng thm ha kh
ln (Benzen: 36kcal/mol, Naphtalen: 61kcal/mol). V vy i vi mt hp cht thm phn
ng th xy ra d dng hn phn ng cng, do trong phn ng cng h thm b ph v.
Nhng phn ng th vng benzen c th l th electrophin S
E
Ar, th nucleophin S
N
Ar hoc
th gc S
R
Ar. Tuy vy, do vng thm c mt in tch cao v d tng tc vi tc nhn
electronphin, cho nn phn ng th c trng v ph bin hn c cc hp cht thm l th
electrophin S
E
Ar.


CHNG II. I TNG V PHNG PHP NGHIN CU

2.1. I TNG NGHIN CU
Trong mt phm vi hp, i tng nghin cu ca lun vn ny l nghin cu cu trc v
tnh cht ca khong 70 cht thuc dy dn xut ca halogen, ancol, phenol, axit cacboxylic:
2.1.1. Dn xut halogen
,
CH
3
X, C
2
H
5
X, CH
2
=CHX, CH
3
CH=CHX. Trong X: H, F, Cl, Br, I
2.1.2. Ancol
CH
3
OH, C
2
H
5
OH, XCH
2
CH
2
OH
Trong X: H, F, Cl, Br, I
2.1.3. Phenol

Trong X: H, F, Cl, Br, I
2.1.4. Axit cacboxylic

CH
3
COOH, XCH
2
COOH, C
2
H
5
COOH, XCH
2
CH
2
COOH
Trong X: H, F, Cl, Br, I
2.2. PHNG PHP NGHIN CU
Phng php s dng nghin cu trong lun vn ny l cc phng php tnh ton l
thuyt ha hc lng t. Khi s dng phng php tnh ton ha hc lng t vi mc
gn ng tt th cc kt qu v cu trc hnh hc, phn b in tch v phn b electron l rt
c gi tr. Ngoi ra, tnh ton l thuyt cn cung cp gi tr kh chnh xc v nng lng, cc
thng s nhit ng nh nhit to thnh, i lc electron, nng lng ion hatng i ph
hp vi kt qu thc nghim.


CHNG 3. KT QU V THO LUN

3.1. LA CHN B HM V PHNG PHP TNH
Hu ht cc thng s lng t ph thuc vo cu trc hnh hc ca phn t. Ngi ta
chp nhn cu trc vi trng thi nng lng ton phn nh nht nh m hnh tn ti trong
thc t. T cu hnh ti u ha hnh hc, chng ti tnh c cc thng s lng t quan tm:
nng lng phn t, mt in tch, di lin kt, rt ra mt s quy lut v tnh cht
ca cc dn xut halogen, ancol, phenol, axit cacboxylic.
S dng chng trnh Gaussian 03 (cng s h tr ca Gauview 5.0) tm cu trc
ti u v nng lng ca phn t C
6
H
5
COOH vi cc phng php tnh v b hm khc
nhau. Kt qu thu c c trnh by bng 3.1.
Trong bng 3.1, cc phng php tnh c chnh xc tng dn t trn xung di,
cc b hm c chnh xc tng dn t tri qua phi. Nng lng ca phn t c tnh theo
n v kcal/mol.
Qua kt qu tnh ton th hin trong bng 3.1, chng ti rt ra c phng php tnh
t ct trn xung ct di, chnh xc tng dn, b hm v b hm va cho kt qu chnh
xc, va chp nhn c v thi gian tnh l phng php DFT (B3LYP) vi b hm c s l
6-31G.
Do , t kt qu kho st cc phng php tnh v b hm c s, chng ti chn
phng php DFT (B3LYP) vi b hm c s l 6-31G tnh cc thng s lng t cho cc
h nghin cu

Bng 3.1. Kt qu tnh nng lng (kcal/mol) trong phn tnh vi vic la chn b hm v
phng php tnh khc nhau bng phn mm Gaussian03 phn t C
6
H
5
COOH.
B hm
Phng
Php
3-21G 6-31G 6-311G
HF
-261033,97600
2 ph 56s
-262391,47813
2 ph 53s
-262447,90293
8 ph1s
LSDA
-261192,60173
5ph 21s
-262557,80328
10ph 22s
-262633,74333
15ph 8s
BPV86
-262627,10438
8ph 19s
-264014,82690
13ph25s
-264080,63283
15ph 53s
B3LYP
-262609,85440
10 ph 23s
-263992,68870
10 ph7s
-264058,45698
18 ph 1s
B3PW91
-262509,97523
11ph 47s
-263891,36000
12ph 38s
-263951,94513
18ph 4s
MPW1PW91
-262545,29720
10ph 55s
-263927,22790
12ph 4s
-263986,83413
17ph 36s
PBEPBE
-262298,86540
7ph 41s
-263687,29073
9ph 49s
-263750,80000
15ph 10s
HCTH
-262558,94533
20ph 56s
-263951,07290
17ph 54s
-264012,43613
27ph 6s
MP2
-261028,66735
8 ph 12s
-262384,84545
7 ph 40s
-262441,52753
57 ph 55s

3.2. TNG HP KT QU V THO LUN
3.2.1. Benzen v dn xut ca benzen

Bng 3.2. Mt in tch trn nguyn t C ca benzen v dn xut halogen ca benzen.
C
6
H
6
C
6
H
5
F C
6
H
5
Cl C
6
H
5
Br C
6
H
5
I
C1 -0,019925 0,028409 0,036996 0,032728 -0,034502
C2 -0,019946 -0,113619 -0,067037 -0,078784 -0,156479
C3 -0,019757 0,520048 0,440027 0,383409 0,291205
C4 -0,019925 -0,113612 -0,067037 -0,078780 -0,156467
C5 -0,019945 0,028408 0,036997 0,032730 -0,034500
C6 -0,019757 -0,071058 -0,008138 -0,010723 -0,035377

Nhn xt
- Trong phn t C
6
H
6
mt in tch phn b u trn 6 nguyn t cacbon.
- Trong phn t C
6
H
5
X, mt in tch trn nguyn t cacbon cc v tr lin kt vi X (C3)
dng hn mt in tch trn cc nguyn t cacbon khc. Do , lin kt gia C X b phn
cc mnh. phn cc ca lin kt gim dn theo dy C F > C Cl > C Br > C - I. KQ ny
hon ton ph hp vi c s l thuyt v kt qu thc nghim.

- Loi hp cht ny ch phn ng trong iu kin rt khc nghit (nhit , p sut cao)
Bng 3.3. Nng lng phn t, mt in tch trn nguyn t C (C-X), nguyn t X, di
lin kt C X ca benzen v dn xut halogen ca benzen.
Cht
Nng lng
(kcal/mol)
Mt in tch
trn C (C-X)
Mt in tch
trn H hoc X
di lin kt
C-X hoc C-H
(
o
A )
C
6
H
6
-145704,67140 -0,019757 0,019887 1,09968
C
6
H
5
F -207961,22545 0,520048 -0,496813 1,35000
C
6
H
5
Cl -434088,54439 0,440027 -0,371808 1,76000
C
6
H
5
Br -1758989,76102 0,383409 -0,280580 1,91000
C
6
H
5
I -4465717,02158 0,291205 -0,140580 2,10000

Nhn xt:
-Nng lng phn t ca C
6
H
6
v dn xut halogen ca n c nng lng phn t m dn theo
th t:
C
6
H
6
> C
6
H
5
F> C
6
H
5
Cl> C
6
H
5
Br> C
6
H
5
I.
Do bn ca phn t tng dn:
C
6
H
6
> C
6
H
5
F> C
6
H
5
Cl> C
6
H
5
Br> C
6
H
5
I
- Mt in tch trn nguyn t cacbon tng khi c nhm th halogen theo th t:
H < I < Br < Cl < F.
Mt in tch trn nguyn t halogen m hn nguyn t hiro. Mt in tch trn nguyn
t halogen m dn t I n F. Do phn cc ca lin kt tng dn t C I n C F.
di lin kt tng dn:
C H < C F < C Cl < C Br < C I
Lin kt cng phn cc, tnh ion cng cao, lin kt ion cng bn. di lin kt cng
ln, cng d b t. Do kh nng tham gia phn ng th (v d bng nhm OH), tng dn t
C
6
H
5
F n C
6
H
5
I, ph hp vi thc t kh nng phn ng ca cc hp cht .
3.2. 2. Toluen v dn xut halogen ca toluen
Nhn xt:
- Nng lng ca cc phn t gim dn :
C
6
H
5
CH
3
> F-C
6
H
4
CH
3
> Cl-C
6
H
4
CH
3
> Br-C
6
H
4
CH
3
> I-C
6
H
4
CH
3

- Mt in tch trn nguyn t cacbon lin kt vi halogen dng hn so vi nguyn t
cacbon tng ng cng v tr trong phn t toluen. Mt in tch trn nguyn t
halogen m dn t I n F. Nh vy, nhm th halogen lm gim mt in tch trong
vng lm tng phn cc ca lin kt
C X. Tnh ion ca lin kt tng, lin kt cng bn. Do phn ng th xy ra cng kh
khn.
- di lin kt C-X tng t I n F. V th, bn lin kt C X gim dn theo dy:
C I < C Br < C Cl < C F
Do , kh nng th tng dn theo th t: F < Cl < Br < I. mi dn xut halogen ca
toluen, lin kt C X v tr meta l phn cc nht, tnh ion ln nht nn bn nht. Lin
kt C X cc v tr octo v para t phn cc hn. Kh nng tham gia phn ng th tng,
ph hp vi thc t.
3.2.3. Kh nng thy phn ca dn xut halogen
Bng 3.24. Nng lng, mt in tch trn nguyn t C (C-Cl), mt in tch trn
nguyn t Cl, di lin kt C-Cl ca mt s dn xut clo.
Cht
Nng lng
(kcal/mol)
Mt in
tch trn C (C-
Cl)
Mt
in tch
trn Cl
di lin
kt C-Cl
(
o
A )
CH
2
=CH-CH
2
Cl -1515831,01953 0,51234 -0,43900 1,92596
CH
3
-CH
2
Cl -338467,92476 0,45192 -0,39299 1,90358
C
6
H
5
Cl -434088,54439 0,44003 -0,37181 1,76000
CH
2
=CHCl -337688,40491 0,36477 -0,34425 1,82368

Nhn xt:
- Mt in tch trn nguyn t cacbon gn vi nhm th halogen gim dn theo th t:
CH
2
=CH-CH
2
Cl > CH
3
-CH
2
Cl > C
6
H
5
Cl > CH
2
=CHCl. Mt in tch trn nguyn t
clo tng dn cng theo th t . V th, phn cc ca lin kt C Cl gim dn, kh
nng tham gia phn ng th bi nhm OH trong phn ng thy phn gim dn.
- di lin kt C Cl ca CH
2
=CH-CH
2
Cl ln hn ca CH
3
-CH
2
Cl ln hn ca C
6
H
5
Cl
v xp x CH
2
=CHCl nn kh nng thy phn gim dn.
Kt lun:
Cc kt qu trn hon ton ph hp vi thc nghim:
- Kh nng phn ng thy phn gim dn theo th t
CH
2
=CH-CH
2
Cl > CH
3
-CH
2
Cl > C
6
H
5
Cl ~ CH
2
=CHCl
C th nh sau:
CH
2
=CH-CH
2
Cl hay anlyl halogenua ni chung b thy phn khi un nng.
CH
2
=CH-CH
2
Cl + H
2
O

o
t
CH
2
=CH-CH
2
OH + HCl
Etyl clorua hay ankyl halogenua ni chung khng b thy phn khi un nng, ch phn
ng vi dung dch NaOH khi un nng.
CH
3
-CH
2
Cl + NaOH
o
t
CH
3
-

CH
2
OH + NaCl
Vinyl halogenua v phenol halogenua ch b thy phn bi dung dch NaOH c nhit
cao v p sut cao.
CH
2
=CH-Cl + NaOH
c
o
t cao
p cao
CH
3
CHO + NaCl
C
6
H
5
Cl + NaOH
c
o
t cao
p cao
C
6
H
5
OH + NaCl
3.2.4. nh hng ca gc ankyl n tnh axit ca axit cacboxylic

Bng 3.25. Nng lng, mt in tch trn nguyn t O (O-H), di lin kt O H
ca mt s axit cacboxylic.
Cht
Nng lng
(kcal/mol)
Mt in tch
Trn O (O-H)
Mt in
tch trn H
HCOOH -119022,46036 -0,669871 0,286062
CH
3
COOH -143701,03042 -0,700114 0,278652
C
2
H
5
COOH -168364,11397 -0,701616 0,278793
C
3
H
7
COOH -193021,65305 -0,712558 0,277326

Nhn xt:
- Nng lng phn t tng dn t HCOOH n C
3
H
7
COOH.
- Mt in tch trn nguyn t oxi ca nhm OH m dn t HCOOH n
C
3
H
7
COOH, cn in tch dng trn nguyn t hiro gim nn phn cc ca lin kt
O H gim dn do gc ankyl y electron v pha nhm cacboxyl, do kh nng t
lin kt O H trong cc phn t axit gim dn, nn tnh axit yu dn theo dy:
HCOOH > CH
3
COOH > C
2
H
5
COOH > C
3
H
7
COOH

3.2.5. Tnh linh ng ca nguyn t hiro trong nhm OH

Bng 3.26. Nng lng, mt in tch trn nguyn t O (O-H), di lin kt O H
ca mt s hp cht cha nhm OH
Cht
Nng lng
(kcal/mol)
Mt in tch
trn O
(O-H)
Mt
in tch
trn H (O-
H)
di lin
kt O-H
(
o
A )
C
2
H
5
OH -97256,33708 -0,567682 0,218068 0,97811
C
6
H
5
OH -192886,09423 -0,688151 0,284833 0,97640
CH
3
COOH -143701,03042 -0,700114 0,278652 0,98222

Nhn xt:
- C
2
H
5
OH c nhm etyl l nhm y electron lm gim phn cc ca lin kt O
H. C
6
H
5
OH gc phenyl ht electron lm tng phn cc ca lin kt O H.
CH
3
COOH, nhm cacbonyl ht electron lm tng kh nng phn cc ca lin kt O
H, nhng ng thi nhm metyl li y electron lm gim kh nng phn cc ca lin
kt O H.
- Nhng iu phn tch trn ph hp vi nhng kt qu thu c bng 3.26.
Kt qu tnh ton l thuyt thu c gii thch tnh linh ng ca nguyn t hiro ca
nhm OH tng dn theo dy C
2
H
5
OH < C
6
H
5
OH < CH
3
COOH. iu ny c khng
nh bng cc kt qu thc nghim thu c di y:
- Phenol c tnh axit yu hn axit axtetic, mnh hn ancol etylic. C th l:
- C
2
H
5
OH ch phn ng vi kim loi kim, khng phn ng vi dung dch kim.
C
2
H
5
OH + Na C
2
H
5
Na +
1
2
H
2

- C
6
H
5
OH khng nhng phn ng vi kim loi kim m cn phn ng c vi
dung dch kim mnh, v d NaOH:
C
6
H
5
OH + NaOH C
6
H
5
ONa + H
2
O
Tuy vy, C
6
H
5
OH l axit rt yu, khng lm i mu qu tm.
- Axit axetic c y cc tnh cht ca mt axit, tuy vn l axit yu. Axit axetic tc
dng vi nhng kim loi ng trc hiro, dung dch kim, mui cacbonat v lm i
mu qu tm thnh .

3.2.6. Quy tc th vng benzen


Bng 3.27. Nng lng v mt electron trn cc nguyn t cacbon vng benzen ca
phenol v axit benzoic.
Cht
Mt electron trn nguyn t C
Octo Meta Para
C
6
H
5
OH -0,144434 0,069020 -0,122421
C
6
H
5
COOH 0,009942 -0,067460 0,041965

Nhn xt:
- phn t phenol, mt electron trn cc nguyn t cacbon cc v tr octo v para m
hn mt electron trn nguyn t cacbon v tr meta. Do trong phn ng th, cc ht
mang in dng (nh Br
+
, NO
2
+
,.) hng vo cc v tr octo v para, thay th ng thi
cc nguyn t hiro cc v tr .
- phn t axit benzoic, mt electron trn nguyn t cacbon v tr meta m hn mt
electron trn nguyn t cacbon ti cc v tr octo v para. V vy, cc ht mang in dng
hng vo v tr meta th nguyn t hiro v tr .
Kt qu thu c trn hon ton ph hp vi thc nghim v ng vi quy lut th vo
vng benzen.
V d : Phenol khng nhng tc dng c vi Br
2
nguyn cht m cn tc dng vi nc
Br
2
, ba nguyn t hiro cc v tr octo v para b th ng thi.



Br
2 (dung dich)

+ trng


+ 3HBr

Phenol 2,4,6-tribromphenol



KT LUN

Sau mt thi gian nghin cu, chng ti thu c mt s kt qu chnh nh sau:
1. Chn c phng php bn kinh nghim thch hp DFT B3LYP ca phn mm
Gaussian 03 tnh cc tham s ha hc lng t cho cc hp cht dn xut halogen,
ancol, phenol v axit cacboxylic.
2. Tnh c cc tham s ha hc lng t ca cc nht nu trn. Kt qu thu c gm:
- Hnh hc phn t: cu trc hnh hc phn t, di lin kt,
- S phn b mt in tch trn cc nguyn t
- Nng lng ton phn
ca cc cht nghin cu. Trn c s xc nh hng phn ng.
3. Kho st quy lut phn ng trn c s nh lng bng cc tham s lng t thu c
trn. Kt qu tnh ton hon ton ph hp vi kt qu thc nghim. l:
a. Phn ng thy phn ca cc dn xut halogen tng dn theo dy:
vinyl, phenyl, halogenua-ankyl halogenua-anlyl halogenua
b. Tnh linh ng ca nguyn t hiro nhm OH tng dn theo dy:
C
2
H
5
OH, C
6
H
5
OH, CH
3
COOH.
c. Tnh axit gim dn theo chiu tng dn ca gc ankyl:
HCOOH CH
3
COOH C
2
H
5
COOH - C
3
H
7
COOH
Nhng kt qu thu c ca lun vn c thc nghim khng nh. iu cho thy
ha hc l thuyt (cu to cht, ha hc lng t) vi s pht trin ca cng ngh thng
tin c th i trc mt bc nh hng cho cc th nghim cn thc hin.



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