DSpace at VNU: Nghiên cứu sự tương quan giữa cấu trúc điện tử và khả năng ức chế ăn mòn của dây dẫn xuất pyridin

\
/,

,
1

T

jl TlCl{rr^
-j

ilt-i
ffis

'rgr{is$c$

HQl
KHoA
HocKTIHUAT
IHAN
riGH
HtlA,
ri uAsNHngcu6rNAM
VIETNAM
ANALYflCAL
SCTENCES
SOC|ETY

r$sN -0868 -3224

Trg

4
2004

HA NOI


Tap cht Ph6.n tr,chH6a, Ly ud.Sinh hoc - Td.pg, s6'4 - 2004

NGHTEN
CUUSUTUONGQIJANGITACAUTRUCOIFr.r
rfi

VAKHAruAruc
UccHE.Aru
ruoNc&a oAypAruxunr PYRIDIN
D€n tba soan 31 - 5 - 2004
Pharn Vin Nhi6u, Vfr Phddng Li6n
Trxdng Dai hoc Khoa hqc TV nhi|n
Vfr Hirng Sinh
ViAnHoa hoc cong nghiep
SUM}IARY

STUDYTHE CORREI,ATION
BETWEENELETRONiCSTRUCTUREAI{D
INHIBITOR EFFICIENCYOF PYRIDINEDERTVATIVES
Using inhibitors to preuent metals from corrosionis a simple and uery effectiueway.
Howeuer,the effectiueinhibitor for each kin,d of materials and certain enuironmentmust
befound. The researchon the relation betueenelectronstructure and corcosion(inhibited,)
inhibition possibility on the basis of semi-quantumcalculation method combined with

multiple regression,allows us to predict, eL'enfind the bestanti-corrosioninhibitors and,
mahefurther plans for practical useand. intlustries.

nrdoAu

rrong trlng m6i tnrong cq thd. Dd girim b6t

Sr: en mdn kim loai ldm thi6t hai ldn

kh5 khdn vd t6n k6m vd kinh rd cho c6c rhi

cho n6'n kinh td qu6t dAn. Nghidn ciru, tim
c6c giAi ph6p ch6ng An mdn, bAo vO kim

nghiOmtdng hop chdt rrc ch€'.cAn c6 nhr3ng

bio vQkim loai. phrrongphrip srl dung chdt
itc che dang duoc rlng dung mdt c6ch rdng

Trong bAo c6o ndy chring tdi trinh bdy
kdt quA nghiOn ctu mdi quan h6 girla cau

r6i do vi6c srl dung thuAn loi vi d6 ddng
hdn so v6i c6c phtiong phAp khdc. Vdn dd

trric diOn trl cria c6.cchat r1cchd v6i hi6u
suat rlc chd an mdn cria chring [1, 4, 5]

dat ra li cdn phii tim duoc chdt irc chd c6

bang phuong phAp tinh to6n b6n h-tongtr3
va hdi qu,vda bidn.

tinh toAn lj thuydt tnJdc Od iam co s& cho
loai ld nhi6m vg c{p b6ch dat ra cho c5.c vi6c dinh hu6ng t6'ng hop c6c chdt c6 khi
nhd khoa hoc. Trong s6 c6c phrrongph6p ning rlc chd an mdn t6t nhdt.

hieu quA nhat cho hlng loai vAt li6u vd
oA

LA


Bao cdogdm:
,
llghr0n cUu mor quan ne g"iuacau truc
dien trl v6i khi nang r1cchd an mdn Fe
trong mdi trddng HrS cua pyridin vd
dAn xudt melyl pyridin 3 cdLcvi tri
khAc nhau bing phtiong phdp OU:
lrtong tt kdt hop v6i phrrong ph6p hr)i

nlng ldm chdt rrc chd an mdn tol, thrrbng
drravdo 3 ti6u chi sau:
- Chdt d6 phii on clinh (bdn) trong didu
ki6n lim ric chd.
- Tao mb.ngbam chat rr6n bd mdt vat
U"o uC
"d.,
Dd che phri t6't

qui da bidn.

C6c ydu to tr6n c6 srl li0n h9 chat chd
v6i c6c thdng sd c{u tnic di6n tr} cria phAn
trr. PhAn mdm HyperChem ?.0 la Phdn

Drr do6n khi n6ng r1c chd dn mdn cua
c6c dAn xuat kh5.c cua pyridin.

PHIJONG PHAP NGHIEN CUU

mdm ding dd thiet ke phAn tli. t6i rJuh6a
hinh hoc vd tinh c6c ihdng sd luong tr.tcua
P5rridinvd c6c dan xudt ciia pyridin Ih
phAn tu rat ti6n loi, d6 sii dung va cho ker
nhting chat c6 kha nang ric chd An mdn.
qua d6ngtin cAy [8].
Ket quA thttc nghiOmda minh chrrng die'u
d6. Ngudi ta do khA ndng rrc chd h.n mi)n
1- Trudc hdt cdn khAo s6t lua chon
- t6'cdd dn mon g/m2h)Fe cria pyridin phrrong ph6p tO'i rlu h6a hinh hgc vh
(R"o""
vd c6c ddn xu{t cria pyridin trong mdi phrrongph6p tinh phi hop cho pyridin vi
trudng dung dich HrS bdng phtiong ph6p c6c clAnxuat cua pyridin. Chung tdi de toi
trong luong vdi c5.c mAu th6P :20 riu h6a hinh hoc vd tinh cActhong so iuong
( d = 2 0 m m )b. d d e i ' b = 1 . 5 m m in d n g d d c h { t trl crla phAn trr p5'ridin bang tat ci' cac
HrS: 3.0mg/1[a].
r1cchd:5 x 10-3g-mol/l;
phrrongph6p b6n h:ong tri c6 trong phfin

quA thu
Khi ning r1cchd in mdn cria m6t chdt mdm HyperChem 7.0. M6t so kdt
phu thu6c vho thhnh phdn h6a hoc, cr{u duoc dem so sAnh v6i sd ii6u thr:c nghidm
[71'iuou iiria ra t,rongc6c bAng I vd 2'
truc phAn tt. DC d6nh gi6 mdt char-c6 ktii
Bd.ng 7. Cdcg6c liAn hA|




115.708

118.431

118.900

121..162

121.516

I l D . / / /

119.056

119.283

t20.692

123.538

114.569
115.9

117.969
118.5

719.729

121.333
121.3


Phuongph6p



AM1

L17.231

r23.504

Plv{3

l1v.D / r11n

ZINDO 1
Ii6u t7l

Otr'7

116.8

123.9

,I -TiJ.J

Bd.ng 2. DO d.ditiAn hA?ud m\men ltong c@ (D)
PhrrongphSp
AM1

N - \ , e

L.3474

C.-Cu
1.396

Ua -

rrll

1.09'4
,i

C . ,- H t o

L)

Cr-C,

Cr-Ht

1.4071

L.7047

1.0995

1.974

1.0948

I.Y,J O

2.387
2.215

PM3

1.3529

r.391

r.0943

1.3954

1 noio

ZINDO 1

1.3501

1.393

r.0942

1.3905

1.0979

1.0965

Tdi Ii€u IL?iI l

1.340

1.394

1.081

1.395

1.084

1.077

r ) A

Lr)


2. Sr1dung phrrongphAp ZINDO1 dd toi
r:u h6a hinh hoc vi phrtong phip AM1 dd
tinh c6c th6ng sd h6a lrrong tri cia ddy
pyridin thd. Kdt qui thu Cr.toccho 6 cilc
bAng3,'4.

Tir c6c sd liOu & bAng 1 vd 2 ta nhAn
thdy tdi rru h6a hinh hoc bang phr:ong
ph6p ZINDO1 vd tinh c6c thdng sd bing
phrrong ph6p AM1 cho kdt quA tdt nhdt
(phn hop v6i thdc nghi6m).

Ci{i

T,o

i1,r-..-cos.-*rr,\

ti

nr(.-\r.CH,

/-\r-at3l\

t-il

|t

n.,'cu'*7iz',,,\*y' \*y'

(r)

H:\r\

t

il

t

\*Aan..

o

il

\*/

F)

t

(4)

r,\

il

t

H,/tNAcH,
(,

i\NAcH,
l l
HiC

(6)

(7)

C6ng thtlc cd.u tao cia pyr;idin ud ctic dd,nxudt cia pyridin
3. C6c rh6ng h6a luong tit tinh drroc, kdt hop v6i c6c gi6'td R}, thrlc nghi6m [4] duoc dua
vio phdn mdm xrl li so 1i6u vd quy hoach h6a thrrc nghiOm STATGRAPiCS 6.0 dd hdi qui da

bidn[e].

Ndt quAvA rHAoLUAN
H.

rY, , . - . ' H

l
.-,'C.:
-..*.'r,'---.a'-'5'

:i
l\
-/
./).r-_-'
v-'..
,..'

li

,/ i
.2.'Dr.-\.-

\//..
N

'.1'..
/
H C

,/ H

r--H
; C H
!

it

H

(c)

(b)

(a)

Hinh I. Ctic d.q.ngbidu d.i\n ph6.n tt 2,4,6- trimetylpyridin sau hhi da t6i ttu hoa hinh hoc:
(a: d'angnJdng, b: dang ciiu, c: dang phdn b6'di€n tich)
Bd.ng 3. Cd'cgid tri ndng ltong cia 7 phd'n tt tran
PhAn trj

sB

-19912.435

- 21107.937

-1195.502

- / / l-vo.ouo

2

-2470r.907

-L477.727

.i00788.660 .23224.ri9
.100946.732 -23224.r79

d

-24699.453

'

^

-28295.84r

.LIDY.Y). I

-28290.720

-L754.796

- 1 2 6 4 8 9 . 6 1 9 .26535.923
- 1 2 6 9 1 3 . 9 2 1 -26535.923

-1757.618
-2037.203

-126338.095 - 2 6 5 3 5 . 9 2 3
-154730.257 -29847.667

7

-28293.542
,31884.871

1L aA nI R
o nI Q
u , L
O

R* tal

D

E"t

I

o

26

n
!bbl

r.979
2.106
r.717

0.388
0.308

0.304

2.239

4.278

1.400

0.250

I . I V

0.194

I

1.779

0.210


Bdng 4. Cd.cthbng s6'ltong tt
. Eru'o

PhAn trl

E"on,o

S(A')

V(A)

Ii
uH

T,noP

0 . 1 8 3 - 1 0 . 0 4 1 9 7 . 6 3 9 3 1 7 . 5 7 3 - 3 I, 1 7

1

.0.i56

z

7.

9.725

ry

-0.203

2.1"32 28.879
1.849

28.769

2.599

33.921 13.395 .0.187

0.208

,9.525 2 7 2 . r 3 9 4 2 1 . 5 0 8 r . 2 1 6
-9.464 269.255 425.186 -0.745

o nl4

a? ?nn

1Q EOR

0 . 15 2

. 9 . 4 3 5 273.1974 2 3 . 8 8 8 -0.924

2 . 3i 6

33.810

1Q ?Oi

0.279

-9.412 3 0 5 . 2 3 8 A ' 7 . 1 ' 1

2.501

38.742

0.165

o

23.838

Po

-9.725 2 3 5 . 4 0 5 '368.786 - 2 . 5 1 0
-v. i,tD
234.286 3 7 r . 2 9 2 -2.233

0.r8r
4

l.bbb

Re

0.400

2

r 1 . 5 6 0 -'0.i'gs
1 1 . 5 6 0 -o.242

-0.280

0-.235

1 5 . 2 3 0 -0.293

Trong d6:
Et,,t,,t: Nd.ng ltgng

t(ing phdn

tt

Momen ltdng

(kcallmol)
En:

Ndng ltong liAn hAt &cal lmol)

E,:

Nd.ngltong electron (kcal lmol)

8,,!

cuc

DiAn fich bd mdt phd.n tJ (A')
Thd tich phan ilx @3)
T

LH,

Nd.nglxqng nguy1n tx (kcal lmol)

logP; log hQs6'phd.nb6'

Ercv6 Ndng ltgng obitan phd,n ti trong P ,
Iop thdp (kcallmol)
Euovr,,:
Ndng luong obitan phd.n tt diiy Ifu
cao (kcallmol)
Pyridin chi:a c6 nh6m the c6 t6'c d6 irr

Ndng luong hydrat hoa (kcal lmol)

Khd. ndng phd.n ctc (A3)

4L,,.

Chi s6'khucxq.(Ar)

LN!

Mfi dA di6n ttch tr€n nguyAnfiJ N

(ndng ltlgng E, d0 phAn cuc D, c6c ydu t6'

suat rirc chd tii 70% Idn 76%; 87%) tudn€t

hinh hoc, ZN diQn tfch trdn nguydn trl
nito,...) cria c6c chdt rrc chd da cir:octfnh
to5.n 3 tren. Phtrdng trinh bidu thi mo'i

rlng vdi c6c chdt 2-metyl pyridin;

quan hOd6 c6 d4ng

mon bang 0.388 g/m2h, s6 grAm xu6'ng
0.304 g/m'h; 0.250glm2h (tfc 1dm tdng hi6u
2,6-

dimetyl pyridin. TOc d0 an mdn cdng nh6

R"o..= const + la,x,

trlc id hiQu dudt trc chd An mdn cirng cao.
'I'oc.d0

An mon gidm cirng v6i Zy.Zy1
giAm trr -0.203 xudng , 0.280 s6 ihm giirn
tdc dO dn mdn tr] 0.388g/m'h xudng
0.250g1m2h hay t6ng srt fc chd trl 7A% l6n
87o/o.
Srl dung phAn mdm STATGRAPHICS
6.0 igl dd thuc hiQn ph6p hdi qui, tim m6'i
quan h6 gita l6c do dn mdn hay hi6u ndng
bAo v6 (R"o".)vdi cAc th6ng sd h6a luong tr:

a1:hOsd cria phrrong trinh hdi qui

*,'ie. ydutd(E,D, S,V,...)i = t "5
Trong thong kO ngridi ta thttdng d,:a uao

g"ie tri

cria he s6' tlidng quan R2[9]

(correlationcoeffient-squared).Gi6 tri cria
dai lrtong nhy thu ditoc cirng vdt const vb'
cil.ca, trong phrtong lrinh tr6n khi tfnh
theo c6cyeu to.


A Tdb dQan mdn phu thu6c uao yd,uj?', S
,7
R.o,,= Rr = 0.713454- 0.001713*S -

8 T6:cd6 d,nmbn phu thu6c ud,oS y6u t6':5,.
Etuuo, Z7{, EHsy6, G

Vdi R! = 0.8061

R"o,. = Rs = -0.6M7 - 0.O03595*5 +
2.019082*Eru*c,'l,+ 2.561361x2,*-+
0.247777*Eno"o + 0.03?546xG

O TOAdQdn mbn phu thu6c ud,o2 y€u t6':S,
Eruro
R.o".= R2 = 0.705581- 0.001941*S

Vdi R2= 0.98b7

+ O,B4E444E"uro

@ T6:cdQdn mbn ph.u tnu6c uarcE yeu t6':S,
zu, G, Eroro, E,

V d i R ' z =0 . 8 1 6 4
g T6c dQdn mbn phu th.u6cud,o yeu
S
t6':S,
Er,n o, Z*

R"o..= R's = - 3.245825- 0.02166?xS+
1.312767*2* + O.023372*G - 0.2109*
Enoro - 0.002799*EB

R"o,. = Rs = 0.?3?943 - 0.001?13*5 +
0.843707*Er,b'o+ 0.7888gg*Zu

Vdi R'?= 0.981b

Vdi R?= 0.9120
O T6:cdQd.nmdn phu thu6c ud,o4 yei to':S,
Errro, Zr, Eron,o

A T6AdQdn mbn phu thu6c ud.o5 yA'ufi': S,
ZN, Eruro, Eroro, E,

R"o"" = Re = 8.902372 - 0.006389*5 +
2.586596*E"uno + 2.112425*ZN +
0.726993*Ello*,u

R"o,. = R", = 4.602395 - 0.01073.3*5+
2.63237*^1 *
1.61BI5*ELU-9 +
0.0941828Enonro+ 0.282g28*En

Vdi R'?= 0.9740

R 2= 0 . 9 7 8 8

Bdng 5. So sdnh gid tri R",,"th4tcnghi|m rd R),,,, h6i qui

MAu.

Ri.,,,,Htii
qui (glmrh)

R"o."TN
p

r!t

D
rLo

rL3

R

D
rLi

pr
IL

5

R",

1

0.388

0.37480 0.38577

L

0.308

0 . 3 1 0 0 9 0 . 3 0 3 0 6 0 . 3 1 2 5 4 0.32003 0 . 3 1 0 6 7 0 . 3 1 0 8 1 0 . 3 1 3 6 0

0.304

0 . 3 1 2 0 9 0 . 3 1 4 0 5 0.29856 0 . 3 0 0 1 5 0.29768 0.29677 0.30822

0.278

0.24715 0.23490 0.26353 0.27093 0.27602 0 . 2 7 5 7 5 0.27516

0.25A

0.25209

o

0.194

0.24534 0 . 2 2 8 3 3 0.21289 0 . 1 9 4 6 1 0.19527

0.19569

0.19303

7

o.2ro

0 . 1 9 0 4 3 0.27040 0 . 2 1 9 4 0 0.27257 0 . 2 1 0 0 0

n ?nqq.c

0.21183

i

R2

0.8061

n aoeAo

0 . 3 8 5 2 4 0.38982 0.39020 0.38404

0.25549 0 . 2 3 1 3 8 0.24847

0.8164

0.9170

0.9740

A

qR.>E t

0.9857

0.2528r 4.24612

0.9815

0.9788

Bing b cho th{y 916tri R2teng ti le v6i sd trinh hdi qui phr; thudc rat nhidu vAo so ydu
ydu to tham gia vdo phrrong trinh hdi qui. to sd ydu td cdng tdng. phutong
trinh m6 ti
didu d6 c6 nghia ld sq phr) hop cua phuong cdngphr) hop v6i thrrc nghiOm(l-rinh2).
2B


phrrong trinh hdi qui (R,,,.,.)vdi cdc t6c d6

1.1

an mdn drtoc xAc dirih bing thr]c nghidm
(R::,) Bhng cdch thay 916tri cAc rh6ng so

y = 0.0517x+().7441t
Rr = 11.9237

,EI

-

a

h6a lrrgng tr] vao c6c phrrong trinh hdi qui,
ta thu dr:oc c6c gi6 tri tdc dd an mdn ly
thuydi (R:,,,,). Bidu di6n srJ tddng quan

L

Y0.e
E
a-

.3o.e

girla R"o""v6i R-,, thinh 3), tr) hinh 3 ta
.Siircu tii

nh4n thdy.gifia hai dai luong R",- vD. R],,,,.

0.7

c6 m6'i trrdng quan rdt chet cho v6i nhau
(ddu c6 R2>0.95)vd phtrong trinh hdi qui
bidu di6n sq phq thu6c gifla R""* vdo c6c
tham so h6a ir-rongtrl cdng chfnh xac khi sd
y'du to cdng nhidu (Dd tin cAy cria phrrong
trinh hdi qui ti 16thuAn vdi sd ydu td rrong
phuong trinh h6i qui).

Hinh 2. S( phV thu6ccia R2 udo so'y€ut6'
trong phttdng trinh h6i qui
Od aann gi6 mirc d6 tr:ong quan vd d6
chinh x6c cria phrrong trinh hdi qui, ta so
s6nh cac 916 tri t6'c d6 dn mdn tinh theo

0.4

R*=0.9585R+0.0'115
K.

3

(' 0.3
:tr
){a

R*=0.9913R+0.0024

R2= 0.9913

= U.95d5

s 0.3
i6

a

T

,3o.z

a

Rcorrth\tc nghi6m
d a

n {

0.4

(B)

(A)

R'=0,9976R+0,0007
* = 0,9976

30

'4O

R " . , ,t h u c n g h r 0 r n

rc)

U.J

Hinh 3. n6 thi bidudi€n m6i txongquan
gitra Rt:!,,- R),,,,
(A):3 y€u t6';(B): 4 y|u t6';(C):5 y1u td
Srl dung c6c phrrongph6p tfnh toen h6a
iuong tt de lr-tachon dd tinh cAc th6ng sd
h6a h.rongtrl cho c6c dAn xudt etyl vd nitro
cria pyridin, kdt hop vdi phr:ong trinh hdi
qui cri.aR".."phq thudc vdo 5 ydu td dtj tinh
du do6n t6'c dO dn mdn cria cSrcdAn xudt
etyl vd nitro cria pyridin. K61 quA thu diroc
cho 6 bing 6.
'llt


Bdng 6. T6:cd6 d,n mbn irrt dodn cir:, m6t
s6'd,6nxud't etyr ud,nitro cia pyrid,in
dxdc tinh qua phtong trtnh h6i qui @ua @
PhAn tr:

E"on o

ZN

G(
0.1983

.0.245

119.006

0.24774

Y . t t t x

0.7712

- 0 .i 9 4

117.592

0.2053

- 0 . 2 i3

0.25857

9.9739

I IO.UOD

0.72937

2-etyl pvridin

254.149

q 71qR

3-etyl pyridin

255.899
9
PhAn trt
J-n

ropyridin
lropvrid n

tropyridin

Atr,'l

S
240.493

E"o'o
. 11 .1 2 0

/-+!, lof

1 1 . 13 7

247.413

r 1.c3L

E
!B

-i354.444

zN
G(-0.0723
I TO.JJ /

1365.458 .0.1383
a 9/rO
l
-0.0983

R"orr€

R"or"6

0.2822-0

117.953

0.24018

1f

4.26017

i

AF.,1

Sri dilng phtrong ph6p ngoai suy d6nh
TAI LIEU THAI{ KHAO
gi6 khi nAng ric che an mdn cria c6c dAn
xudt p1'ridin v6i c6c nh6m thd nucleophin [1]. Trdn Hi6p Hii - Hodng
Van H,:ng. Cc
(-CrH,vd -NOJ 3 cac vi trf rhe khac nhau
ch€'d,nmdn uci.m6i quan hd u6i hoa hoc
cho-th{y 4-etyl pyridin vd 3-nitropyridin cir
Itrng tu - H6i nghi di6n h6a Todn
khi nAng l1c chd An rndn t6t nh{t so v6i cdc:
Quoc(2002).
dAn xuat khac cing ioai nhrrng vi trf nh5m
rl-rekh6c nhau.
l2l. Trdn ThAi Hda, Luan ud,nti\n si hoa
hoc - Trtiong DHKHTN (2002),
Nfl luAN
i. Da tim dr:ocm6i quan h6 girta t6c d6
an mdn v6i cac thong so cau tnic tii6n trl
cua day hop chdt thd crj.a pyridin bdng
phr.rongph6p rinh to6n b6n ldone t& kei
hop vdi phAn cich hdi qui tuydn-ttnh da

bien. C5:cphrrong trinh hdi qui ddu d6ne
tin ca1'(ddu
c 6R 2 > 0 . g ) .
.2. .Gia cri crja he s6'tucrngquan (R) vA
sd ydu td trong phr_iong
trinh h6i,qui tf lQ
thu4n vdi nhau (hirh A, B), trlc ld'ph6p-hdi
qui cdng chinh xdc hon khi s6'ydutdtdng.
3. Phr:ongph6p kdt hop gita vi6c tinh
to6n h6a h"iongtrl vdi hdi qui da bidn dd
khio s6t srr ii6n h6 dinh luong gllta cdu
tric - hhd.ndng itc che rin mdn cria m6t ddy
c6c hop chdt hrlu co, c6 thd cho ph6p tim
dttoc c6c chat c6 khi nang rlc chd dn mdn
tdt hon bdng c5.ch ngoqi suy tr) phuong
trinh hdi qui fting'6).

[3]. i\guy€n Minh Thio, Hoa hoc cachqp
chat di udng. Chrrong b. NXB GD
(2000).
t4l. V.S, Saslri* and J.R. Perumaredd.i**,
Corrosion Science, Vol.50, No.6,
pp.432.437(1994).
i5l. Reza Pavaherdasshii, Anti-Ccr:-osion
Methods and Materials, y6T 47 No.1,
pp.30-34(2002).
[6]. Corrosion inhibitors, Chapter. 10
(2000).
l7l CRC Hand,book of chemistry and,
physics- A ready-reference booh of

chemicaland pltysical data. - Tgthod_
Boca Ratcn N.Y: CRC press,iSBN 08493-0478-4
(1997).

[8]. Hyper Chem Release7.0 for Windows,
4. Tt phrrongtrinh hdi qui ta nhdn tha-v
Molecular
Modeling
Sysiem,
4-etyi pyridin ld chat c6 khi ndng rlc che
FTrrnernrrho T-^
an mdn tdi nhdt (td'c d0 in mdn R""- =
0.12937gim'zh).
[9]. Sfatgraphics6.0 for Dos.
frJ

JU

lJLrvuvv,

rrru!