DSpace at VNU: Nghiên cứu mối tương quan giữa cấu trúc phân tử và khả năng ứng chế ăn mòn kim loại của một số hợp chất axetophenon - aroyl hyđrazon

DHQGHN,
KHTN& CN, T.XXII,Sd 34 PT,2006

NGHTfiN
cw rvrdlrudNc euAr.rcl0e cAu rRUc pHANrrl
*

!

?

v

a

r

v

r

?

A

;

2

vA KHA NANGuC CHn An UON KrM LOAr CUA nnQr SO
Hqp cHAr A)GTorHENoN - ARoyL HTDRAZoN

STUDY ON THE RELATION BETWEEN MOLECULAR
STRUCTUREAND CORROSIONINHIBITION OF SOME
ACETOPHENONE . AROYL HYDRAZONE
Ph4m Vin NhiGu,Vfr Phdong Li6n, LAm Nggc Thi6m
Khoa H6a hgc,Trting Doi hgcKhoa hgc Tt nhiAn,Dgi h4c QuOcgia Hd Nfri
- aroylHydrazonecompoundshave been studiedby
Abstract. Someacetophenone
the inhibitionof coppercorrosionin 3N nitric acid solution.The structureof some
- aroylHydrazonecompounds
acetophenone
wereoptimizedand calculatedby using
the ZINDO/1methodof thequantumchemicalprogramHype€hem7.0.
Resultsof the above calculalionis coordinatedwith inhibitionefiiciency(P) that is
derterminedby experimentation
and bothare appliedto Statgraphicsoftwareto carry
out linearregression.

1. M& ddu
An mdn kim lo4i ld sg ph6 huli kim lo4i vi hgp kim do t6c dQngli h6a cfra mdi
trdbng. Hfu qui cia sg in mdn kim logi li lim thay ddi tfnh chdt, suy giim nhi6:uchrlc
n[ng cta kim lo4i vi hgp kim, din t6i giim tudi thq cria c6c thidt bi, c6ng trinh; gAy
nhi6:utdn thdt cho hQ sinh th6i vi ndn kinh td qudc dAn cira bdt ki qudc gia nio. Sg an
mdn kh6ng bao gid ngrbng,nhung ph?m vi vh m(rc dQc6 thd giim dugc nhd c6c biQn
phdp ch6'ng in mdn. Trong sd c6c phttong ph6p bio vQ, chdng in mdn kim loai thi
phrrong ph6p srl dgng chdt rlc chd dang dugc itng dgng m6t c6ch rQng rdi do viQc st
dung thu{n lgi vA d6 ddng hon so vdi chcphrrongph6p kh6c. V{n d0'd{t ra lA: phii tim
dtrgc ch{t irc chd in mdn c6 hiQu qui nhdt cho ttng lo4i v{t liQu vd trong tirng mdi
trddng cq thd.[Z]
lrl0ngqt c0acic phlnt&
Blngl. Cic 916trining lUlng,nhlfthinhthlnh,momen

2

AH
e
u
E*,
Eo
-76/,5.47
-675651.56
-129495.59 -11463.38
9.483
-7506.22
-647298.29
-'t2c356
-11324.13
34
9.431

3

-'t29356,84

4
5
6

-565776.92 -7382.04
-567240.31 -7217.54
-724995.07 -8194.99

7

-108879.29 -11185.04
-112364.69 -10915.00
-134455.60 -12288.00
-134316.30 -12148.69

I

-134316.78

-592010.78 -8056.17

Phint&
I

11324.63

-12149.17

-644626.51

-7506.72

4.745

5.353
8.210
9.069

-695062.09 -8055.68 9.000
4.459


PhanVln Nhi0u, V[ PhucngLi0n, l-trm Ngqc Thi€m

142

-117324.58 .11739.48 -613583.30
-111616.76 -12366.41 -600030.39
-140162.44 -11660.07 -731822.83
-140022.83 -11520.47 -701387.11
-1400238?
-11521.46 -698765.04
-117324.04 -11738.94 -606799.98
-123031.91 - 1 1 1 1 2 . 0 6 420326.03
-119546.33 -11381.92 -618942.53

-7766.94 7.766
-8178.33 6.190
-7782.60 10.1
16
-7&f3.00 10.593
-7643.99 4.661
'14
-7766.40
8.427
-7355.04
10.099

15
-7519.37
6.934
16
E":Ninglugng
Er:NlnglucngliOnkdt (kcaUmol);
trongd6: E*: Ninglugngt6nghqpc0aph0nt0 (kcaUmol);
(kcal/rnol);
p: Momen
c (D).
(kcal/mol);
lu6ngcu.
hinhthAnh
electron
AH:NhiQt
9
10
11
12
13

Trong ddi sdng vi ki thuft, Cu vh hgp kim cfra Cu drrgc srl dgng trong c6c hQ
thdng nhiCt, c6c b6 phfn ngrrng tg hoi nttdc, ... CAchQthdng niy thudng bi bao phir bdi
c6c l6p cacbonatvir oxit. Tr6n thqrct6, ngudi ta thudng dtng c6c dung dich axit HNO3
ho{c HCI dC tam s4ch c6c b€'m{t niy. Nhrrng trong m6i tnrdng axit hay nu6c tg nhi6n
(c6HCO3', CO, , OJ, Cu vi hgp kim cria Cu d6 bi hda tan thirnh Cu2*.MQt trong sdc6c
hrr6ng ad Ur6c phgc sg 6n mdn Cu trong c6c m6i trttbng d6ln s& dung chdt rlc chd. C6c
chdt irc chd in mdn thrJdngdugc srl dung lA cic hgp chdt hflu cclc6 chira c6c nguy6n td
O, N, S, P. [4, 5]. C6c c6ng trinh nghiOn ciru gAn dAy [1, 3] cho thdy cic hqp chdt
axetophenonaroyl hydrazon c6 khi ning fc chd dn mdn kim lo4i Cu trong m6i trddng

axit HNO3 3N cao.

2, Th{c nghiQm
S& dgng phdn mdm Hyper0hem ?.0[8] ad ffrio s6t cdu trric phAn trl cria c6c hgp
chdt axetophenonaroyl hydrazon bing phrrong phip b6n kinh nghiQm. X6c dinh khi
ndng rlc ch6'qu6 trinh in mdn Cu trong m6i truing axit HNO3 3N cfra c6c hqp chdt
axeto phenon aroyl hydrazon bing phrrong ph6p diQn h6a, srl dUng dudng cong phAn
cgc. CAc th6ng sO'lrrgngtrl thu duqc tr} tinh to6n kdt hgp v6i hiQu sudt irc chd in mdn
@) th{c nghiQm drrgc drra vdo phdn m6'm Statg:raphic dd thgc hiQn ph6p hdi qui da
bidn. Ngoqi suy trf phrrong trinh hdi quy da bidn dd: dg do6n dugc khi ning rlc chd 6n
mdn Cu trong m6i trtidng axit HNO3 3N cfra c6c d6n xudt kh6c cfra lo4i hgp chdt hfru cd
trOn, ddng thdi c6 thd kidm tra l4i dd tin cqy cria phrrongtrinh hdi qui thu drrgc.Cin crl
vio cdu trfc cfra c6c hgp chdt nghi€n cfu chring t6i de tfnh to6n c6c th6ng sd lrrgng trl
bing phrrongph6p ZINDO/I cho mQts0'phdntrl axetophenonaroyl hydrazon.
Blng2.MQtsdttramsdc{u tr0c
Phdnt(t
,l

Err*
4.269

houo
-3.719

2
3

4.306

-6.402

4

5.527

-6.083

5
6

5.667

-5.946

7

3.805
4.289
4.320

-6.422
-3.695
-6.246

S

405.801
445.381
448.344
374.803

V
811.998

824.247
823.574
788.552
394.409 783.752
447.870 863.966
487.114 875.350


NghiOncftr mdi tuongquangiila cdutnic phAntir...

15

3.820
5.689
5.686
4.190
4.293
3.750
5.547
5.559

16

5.404

I

I

10
11

12
13
14

14.3

-6.269

-5,818
-5.869
-3.794

-6,307
-6.335
-5.950
-5.903
-6.067

490.121
436.167
477.31',1
423.524

874.791

465.892

845.746

836.118
869.255
834.552
462.830 846.692

452.950 838.921
41't.910 805.833
392.325

811.081

phint0chuabichidm
trong
d6:Err*: Ningluong
phintfichuabicfri6m
obitan
thdpnhdt;Ero*:Ninglucrrg
obitan
thdpnhdt;
S:Di€n
tichb€mftc0aphdn
t01i'y;V:Thdtichprran
fi 1i'y.

3. Kdt qua vi th&o lufln
C6c phdn trl mA chring t6i tidn hdnh nghiOncrlu bao gdm:

R-o_,m_,p_NOr;o_OH:o_NHr

(r) (2) (!)

(r)

(1)

l.o_,n_,p_NOr;o_OHi6_CHr

(6) (r) (r)

(e)

(io)

R-o_,r_,9_NOz;o_OHir_Cll!;o_NHr

0r) 0r) (r)

0r)

01)

05)

3.1. Khio s6t cdu trfrc phAn tr? cria 16 hqp chdt axeto phenon benzyl
hydrazon biing phrldng ph6p bin kinh nghiQrn ZINDO/I. Cic tharn sd
lrr{ng ttl thu dtr{c tfi tinh toAn dtfec trinh bdy tr6n c6c bing sd liQu | ,2 ,3

Blng3.ilit alQ
dlentlchtr6ncic nguydn
td
Phdnt&
1

2
3
4

5
6
7
I
I

Zn,o,

-0j27

Z n ru.rt

-0.397
-0.456

-0.129
-0.155
-0.154
-0.148

-0.400

-0.163

-0.127

-0.129
-0.154

-0.397

-0.398
-0.398
-0.400
-0.410
-0j28
-0.394
-0.397

-0.153
-0.163
-0.158

Z u ,r-t

-0.137

4.122

-0.123

-0.122
-0.114

-0.137
4.121

-0.122

-0.114

-0.116
10
-0.129
11
4.132
-0.154
-0.114
12
-0.153
.-0.118
13
-0.157
-0,409
-0.111
14
-0.163
-0.400
-0.109
15
-0.148

-0.456
-0.117
16
Trongd6:Zo(uct,Z*(r"),2*rr*,LimitilQdiQntfchtr€nc6cnguy0ntfiOviN0c6cvitrituongr,nrg


PhanVin Mieu, V0 PhucmgLien, LAmNgqcThi€m

144

3.2. HiQu sudt itc chd quA trinh in mdn Cu trong m6i trddng axit HNO' 3N
c&a 16 h{p chdt axeto phenon benzyl hydrazon' ddqc xic dinh theo
phddng ph6p diQn h6a, srl dgng dddng cong phAn c{c. Kdt qui niy drrfc
ghi I bing 4
Blng 4. HlQurudtthYcnghlQm
PMntl

2

I

3

5

I

7

6

I

10

9

HQU
su{t
55.9 56.8 51.9 65.4 64.9 70.6 763 725
ftci6

u.2

1 1 12

1 3 1 4 1 5 't6

88.5 68,5 '6.7 i7A 6.3 t2.2 18.4

3.S. Mdi trfdng quan gifra cdu trric phAn t& vA khi ning irc chd 6n mdn Cu
trong m6i trtldng axit HNO' 3N cria cdc h{p chdt axetophenon benzyl
hydrazon
(rc
C6c th6ng sd thu drrqctir tfnh to6n lrrgng til kdt hgp v6i clc gLetri hiQu sudt
chd 6n mdn kim lo?i cu trong m6i trudng HNOs 3N (x6c dinh bing thgc nghiQm) drrqc

piaf *i* *O hinh h6aud t6i n ndi th4cnghiqmStatsraphic5.0 dd thgc
"i"
hign ph6p hdi quy tuydn tfnh, tim mdi quan he qfl9 hiQu sudt r1cchd in mdn th{c

a""

nghiQmubi.Ac th6ng sdlrrqng trl ctra c6c chdt rlc ch0. [6,7,9]
Phrrongtrinh hdi quy c6 dang:

sudtb6ovQcia cdcchdt(rcchd
P : HiQu
k" : Hf sd ciaphwngtrinhh6iquY

P =f k"X"+const

X^: Cdcydut6 hdiquy(6nhhutng)
Phtong trinh h6i quy cho P sdt udi thge nghi4rn nhdt (*L

= 0.9538)c6 dqng:

-5.76ELUMo
(")
-5l.48ZNH-313.30Z,,'+\.52p+0.25V+38.65EHoMo
p=106.16+1082.862*
Bing 5.Hlgusudtthu-bnghlgmvi Hlgusu{t tyttruydtttreophudngtrinh('}
PhinE

1

2

3

4

5

6

I

I

9

10

11

12

13

14

15

16

88.5 68.5 76.1 67.4 86.3 82.2 884

PTN

5s.9 56.8 51.9 65.4 64.9 70.6 76.8 725 u2

PLT

57.2 58.3 52.1 66.6 66.1 70.5 78.0 71.9 035 884 67.2 77.2 66.8 86.8 82.3 87.3


y=0.9671x+2.5858
R2 = 0.9948

quan
Hinhl. Trrcng
tuydn
tfnhglihPTN
vi PLTtheophtlung
trinh(')
Tir c6c sdliQu thu drrgctrong c6c bing ghi 6 trdn chring tdi nh{n thdy ring:
- C6c th6ng sd nhrr S; V; p hdu nhu it inh hrrSngtdi hiQu sudt irc chd in mdn
(t, = t.szrts = 0.23;kv= 0.25). Trong khi d6 rngt dQdiQntfch trOn cic trung tdm hdp phq
Z*r;Z*riZn l4i inh hudng l6n tdi hiQusudt rlc chd in mdn.
- MAt kh6c khi phAn tfch kdt quA ph6p hdi quy dd chi ra ring vdi cing nhidu ydu
td inh hrrSng cria cdu truc thi kdt quA cia him mr,rcti6u P cing s6t v6i thrtc nghiQm.
Nhfrng kdt qui nly sE gidp ta giai thfch drrgckhi ning dc chd in mdn kh6c nhau cria
cAchydrazon, vh drl do6n khA ning rlc chd 5:nmdn cria mQt sd hydrazon chua dttgc tdng
hqp.
3.4. Dd doin khi ning r?c chd in mdn Cu trong m6i tntdng axit HNO9 3N
cria cAc ddn xudt khAc cfra lo4i hgp chdt hitu cd tr6n
Sil d+tngphttong trinh hdi quy (*) dd ngogi szy ddi vdi mQt sd ddn xudt kh6c cria
lo4i hgp chdt axetophenonbenzyl hydrazon. Kdt qui thu duo.cghi trong bing 6.

Blng6.Hlfusudtbio v{ dr,rdoindw.ctlnhquaphudng

trinhhdlquy('}

STT

R

Zot*l

Z * (t-rl

Z n 1tr=cy Errrc

Eo*

v(i')

tr

PDD(70)

-0.403 -0.157 -0.112 5.394 -6.0r3 809.29110.1V7
1 8 4'-OH -0.415 -0.159 -0.111 5.561 .5.982808.8889.228
1 9 2'-CH. -0.419 -0.159 -0.111 5.582 -5.936 827.655 7.932
20 4'-CH. -0.413 -0.158 -0.1r1 5.545 -5.925 839.3969.180
21 3'-NH, -0.407 -0.156 -0.112 5.565 .5.936824.389 8.633
22 4.NH. -0.420 -0.159 -0.109 5.748 -5.860 824.35510.138
17

3-OH

77.3

81.0
86.8

90.3
83.7
93.7


Phan Vin Nhi€u, Vii

X6t inh hrrfing cira bin chdt nh6m thd vi vi tri cfra n6 d6i v6i hiQu sudt bio vQ
chdng in mdn kim lo4i Cu trong mdi trrrdng HNO3 3N.

'*e-\f-NH-c

I

|,|,IH,

I

C*r,*rltV
Kdt hgp sdliQu 6 bing 5 vA bing 6, chring tdi nh$n thdv:
- HiQu sudt b6o vQ chdng in mdn kim lold r((o)+ (zz)) , P(r)*(s)), vi trong c6c
phAn tir (e)*(zz\ c6 th6m 1 nh6m -CH3hay 1 nh6m --OH (b6n nh6nh tr6i ctra phAn trl)
so v6i c6c ph6n trl (r)+(s). .CHs, -OH, li cic nh6m ddy electron m?nh vho hQ li6n hgp
n6n lim ting m{t dQelectron tr6n c6c trung tdm hdp phr1,lam tdng hiQu sudt flc chd
in mdn.

- D6i v6i nh6m thdR = Noz: P (o-R); P (p-R) < P (m-R). I (R = NOt < P (R = NHz
ddng thbi cdn c6 khi ndng
, CH, , OH), vi nh6m thdNO2 cOdac tfnh 6i electron l6n nhdt
rlc chd
hydrat h6a trong m6i trtrdng axit tr6n b6'mat ddng n6n cing lirm giim khi ndng
6n mdn cria phdn trl.
- Ddi v6i nh6m thdR = NHz , CHr, OH: P (m-R) ;P (o-R) < P (p-'R).PhAntfi chita
cira phAn trl khdng
1p_R)cOkh6 ning irc chdtdt ntrdt vi tphg
v6i b6'm4t kim
hdp
tAm
,ig-#.4" kha nalg phin irng hay hdp phg cria c6c trung
phAn
trl
d6 cin tr8 c6c
gran
cria
io?]. rc"i R A trilm-R) rtav (o-D tni rripu irng kh6ng
"i
phAn
trl c6 khi
phin irng hay q.ra trinh hdp phg l6n b6'm4t kim loai lim
it""Jia*
ning flc chd 6n mdn kim lo4i k6m hon.
- D6i v6i nh6m thd R = NHr, CHg,OH khi E cing c6c vi tri thd -octo, 'meta, 'para
tudng rlng: P LOH) < P LCHJ < P LNH'. N cria nh6m--NH2 c6 thC d6ng vai trd nhd
mQt irun! tdm hoat dQng,ldm ting sd trung t6im ho?_tdQngcria phAn trl ch(ra nh6m
-NH2 n6n

NHr len b'd.,t"rrttg'tam. M4t d0 diQntfch cria nh6m -CHsnh6 hdn so v6i nh6m
mdn cao
in
phan trl chfia nh6m -CH3c6 3 trung tAm ho4t dQngvh c6 khi ning rlc chd
'OH
hdp
t6m
c6 cring sd trung
,rfr.rrrgthdp hon so v6i pitatt tl chira nh6m NH2. Nh6m
theo chi6:utfo -NHr, -9Hr, d6'n-OH c6 tinh bazo giim ddn n€n phdn trl ch(ta
pft\r
"t.i"g
-OH
c6 khi ning itc chdydu hon.
.tt Otn
- PhAn trl hydrazon chita nh6m thd -R ddy electron cing m4nh, vh & v1 tri thO
para s6 cho hiQu sudt bio vQchdng in mdn kim lo4i Cu trong m6i trrring HNOa 3N cao:
I

:N -NH-'C
H

oH

3

tl
o

4. Kdt lu$n
Ket hgp c6c th6ng sdcdu tnic phAn trl dtrgc tfnh bing phrrong phip lrrong trl b6n
kinh nghiQm.v6i c6c k6t qui rlc chd in mdn kim loqi Cu cria mQt
.h{t'hyd"rrorr,
ta c6 thd thidt t$p dttgc phuons trinh hdi quy bidu'di6n -di q.,.o"dtrgp
fre ilru frigu sudt rlc
ch0,5'nmdnCuvic6cth6ngsdcdutrriccriac6cphAntrlhydrazon.
Phrrongtrinh hdi quy thu drrgcs6 grip ta giii thfch dtroc khi ning fic chd 6n mdn
kh6c nhau cia c6c hydrazon, vi drt do6n khi ning rlc chd in mdn cria -qt
nyarazon
"dnhie:u thdi
chrta dugc tdng hgp, 4inh hu6ng cho viQc tdng htp htu co, tidt kiQm dtrgc
gian trong viQctim kidm cht't rlc chd hiQuqui cao d6i v6i Cu.
Khi ning rlc chdin mdn Cu cfra eic hydrazon tr6n phr; thuQcvio m{t dQelectron
tron cac trung tam h{p phr;.trong phin trl. Cing nhi6'u nh6m ddy electron (NH2, -CHr,
-OH) trong phdn trl thi m{t dQelectron t4i cic trung tAm h{p phg cing l6n vi
nri nanl
itc ch6-in mdn cing cao.

TAI LIEU THAM KHAO
tU

Vt Minh Tdn, Tdng hqp mgt sd chdt 2 - hydrory axetonphenon - aroyl hydrozon vd,
nghiOn ctu mdi ttdng quan gita cdu trtc electron ud hhd, nd.ng tc clrd d.n mbn kim loai
cita chrtng, Lu{n vln thqc si h6a hgc, }ili NOi, 2009.

I2l

Reza Favaherdashi,An ti - CorrosionMethodsand Materials, Yol.47, No.l, p.30-34.
Gy. vastag, E.szocs,A.shaban and E.K6tman, Pure Appli. chem, vol.z3, \12(2001),

p.1861- 1869.
H.Baeza,M.Guzm6n, P.ortega and L. Yera, J.chil. chem. soc, v.4g,N.B, conception,
sep.2003.
A.S' Fouda, M.M. Gouda,S.I.Abd El - Rihmn. Bull, (2000),Korean Chem.Soc,Vol.21,
N011,p.1085.

t3l
t4]
t5l
t6l
t7l
t8l
tgl

Corrosioninhibitore (2000),chapter 10
Hond.bookof corrosion. Me Graw . Hill, 1999
Hyperchem Release7.0 for Window, Molecular Modeling System,Hypercule, Inc.
V.S. Sastri and J.R. Perumareddi,CorrosionSci,ence,
Vol.50,No.6(1994),p.432-437.