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 chc p
Trang 1DHQGHN, KHTN & CN, T.XXII, Sd 34 PT, 2006
vA KHA NANG uC CHn An UON KrM LOAr CUA nnQr SO Hqp cHAr A)GTorHENoN - ARoyL HTDRAZoN
STUDY ON THE RELATION BETWEEN MOLECULAR
STRUCTURE AND CORROSION INHIBITION OF SOME
ACETOPHENONE AROYL HYDRAZONE
Ph4m Vin NhiGu, Vfr Phdong Li6n, LAm Nggc Thi6m
1 M& ddu
An mdn kim lo4i ld sg ph6 huli kim lo4i vi hgp kim do t6c dQng li h6a cfra mdi trdbng Hfu qui cia sg in mdn kim logi li lim thay ddi tfnh chdt, suy giim nhi6:u chrlc n[ng cta kim lo4i vi hgp kim, din t6i giim tudi thq cria c6c thidt bi, c6ng trinh; gAy nhi6:u tdn 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 dQ c6 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 chc phrrong ph6p 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]
7 -134316.30 -12148.69 -695062.09 -8055.68 9.000
Trang 2142 Phan Vln Nhi0u, V[ Phucng Li0n, l-trm Ngqc Thi€m
electron (kcal/mol); AH: NhiQt hinh thAnh (kcal/rnol); p: Momen lu6ng cu c (D)
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, CAc hQ thdng niy thudng bi bao phir bdi c6c l6p cacbonat vir oxit Tr6n thqrc t6, 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 (c6 HCO3' , 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 thrJdng dugc srl dung lA cic hgp chdt hflu ccl c6 chira c6c nguy6n td
O, N, S, P [4, 5] C6c c6ng trinh nghiOn ciru gAn dAy [1, 3] cho thdy cic hqp chdt axetophenon aroyl 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 axetophenon aroyl 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
@) 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 phrrong trinh 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
3 3.805 -6.422 448.344 823.574
Trang 3NghiOn cftr mdi tuong quan giila cdu tnic phAn tir 14.3
trong d6: Err*: Ning luong obitan phin t0 chua bi chidm thdp nhdt; Ero*: Ning lucrrg obitan phin tfi chua bi cfri6m
thdp nhdt; S: Di€n tich b€ mft c0a phdn t0 1i'y;V: Thd tich prran fi 1i'y
3 Kdt qua vi th&o lufln
C6c phdn trl mA chring t6i tidn hdnh nghiOn crlu bao gdm:
R - o _ , m _ , p _ N O r ; o _ O H : o _ N H r l o _ , n _ , p _ N O r ; o _ O H i 6 _ C H r R - o _ , r _ , 9 _ N O z ; o _ O H i r _ C l l ! ; o _ N H r
( r ) ( 2 ) ( ! ) ( r ) ( 1 ) ( 6 ) ( r ) ( r ) ( e ) ( i o ) 0 r ) 0 r ) ( r ) 0 r ) 0 1 ) 0 5 )
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
Blng 3 ilit alQ dlen tlch tr6n cic nguydn td
2 -0.397 -0.155 4.122
5 -0.400 -0.163 -0.114
7 -0.398 -0.154 4.121
I -0.398 -0.153 -0.122
14 -0,409 -0.157 -0.111
Trongd6:Zo(uct,Z*(r"),2*rr*,LimitilQdiQntfchtr€nc6cnguy0ntfiOviN0c6cvitrituongr,nrg
Trang 4144 Phan Vin Mieu, V0 Phucmg Lien, LAm Ngqc Thi€m
3.2 HiQu sudt itc chd quA trinh in mdn Cu trong m6i trddng axit HNO' 3N
phddng ph6p diQn h6a, srl dgng dddng cong phAn c{c Kdt qui niy drrfc ghi I bing 4
PMn tl I 2 3 I 5 6 7 I 9 1 0 1 1 12 1 3 1 4 1 5 't6
HQU su{t
ftci6 55.9 56.8 51.9 65.4 64.9 70.6 763 725 u.2 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
chd 6n mdn kim lo?i cu trong m6i trudng HNOs 3N (x6c dinh bing thgc nghiQm) drrqc
a""
"i" piaf *i* *O hinh h6a ud t6i n ndi th4c nghiqm Statsraphic 5.0 dd thgc
hign ph6p hdi quy tuydn tfnh, tim mdi quan he qfl9 hiQu sudt r1c chd in mdn th{c nghiQm ubi.Ac th6ng sdlrrqng trl ctra c6c chdt rlc ch0 [6,7,9]
Phrrong trinh hdi quy c6 dang:
P =f k"X" +const
Phtong trinh h6i quy cho P sdt udi thge nghi4rn nhdt (*L = 0.9538) c6 dqng:
Bing 5 Hlgu sudt thu-b nghlgm vi Hlgu su{t ty ttruydt ttreo phudng trinh ('}
PTN 5s.956.8 51.9 65.4 64.9 70.6 76.8 725 u2 88.5 68.5 76.1 67.4 86.3 82.2 884
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
Trang 5y = 0 9 6 7 1 x + 2 5 8 5 8 R2 = 0.9948
Hinh l Trrcng quan tuydn tfnh glih PTN vi PLT theo phtlung trinh (') Tir c6c sdliQu thu drrgc trong c6c bing ghi 6 trdn chring tdi nh{n thdy ring:
- C6c th6ng sd nhrr S; V; p hdu nhu it inh hrrSng tdi hiQu sudt irc chd in mdn
Z*r;Z*riZn l4i inh hudng l6n tdi hiQu sudt 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,rc ti6u P cing s6t v6i thrtc nghiQm Nhfrng kdt qui nly sE gidp ta giai thfch drrgc khi ning dc chd in mdn kh6c nhau cria cAc hydrazon, vh drl do6n khA ning rlc chd 5:n mdn 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+tng phttong trinh hdi quy (*) dd ngogi szy ddi vdi mQt sd ddn xudt kh6c cria
STT R Z o t * l Z * (t-rl Z n 1tr=cyErrrc E o * v(i')
Trang 6Phan 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
C*r,*rltV
Kdt hgp sdliQu 6 bing 5 vA bing 6, chring tdi nh$n thdv:
- HiQu sudt b6o vQ chdng in mdn kim lold r((o)+ (zz)) , P(r)*(s)), vi trong c6c phAn tir (e)*(zz\ c6 th6m 1 nh6m -CH3 hay 1 nh6m OH (b6n nh6nh tr6i ctra phAn trl)
so v6i c6c ph6n trl (r)+(s) .CHs, -OH, li cic nh6m ddy electron m?nh vho hQ li6n hgp n6n lim ting m{t dQ electron tr6n c6c trung tdm hdp phr1, lam tdng hiQu sudt flc chd
in mdn
6n mdn cria phdn trl
- Ddi v6i nh6m thdR = NHz , CHr, OH: P (m-R) ;P (o-R) < P (p-'R).PhAn tfi chita
,ig-#.4" kha nalg phin irng hay hdp phg cria c6c trung tAm hdp phg v6i b6'm4t kim io?] rc"i R A
ning flc chd 6n mdn kim lo4i k6m hon
,rfr.rrrg thdp hon so v6i pitatt tl chira nh6m NH2 Nh6m 'OH c6 cring sd trung t6m hdp pft\r
.tt Otn -OH c6 khi ning itc chdydu hon
- PhAn trl hydrazon chita nh6m thd -R ddy electron cing m4nh, vh & v1 tri thO para s6 cho hiQu sudt bio vQ chdng in mdn kim lo4i Cu trong m6i trrring HNOa 3N cao:
: N - N H - ' C
t l
H
o
I
Trang 74 Kdt lu$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
"dtrgp .h{t'hyd"rrorr,
ta c6 thd thidt t$p dttgc phuons trinh hdi quy bidu'di6n -di q.,.o fre ilru frigu sudt rlc ch0,5'nmdnCuvic6cth6ngsdcdutrriccriac6cphAntrlhydrazon
Phrrong trinh hdi quy thu drrgc s6 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
chrta dugc tdng hgp, 4inh hu6ng cho viQc tdng htp htu co, tidt kiQm dtrgc nhie:u thdi gian trong viQc tim kidm cht't rlc chd hiQu qui cao d6i v6i Cu
Khi ning rlc chdin mdn Cu cfra eic hydrazon tr6n phr; thuQc vio m{t dQ electron 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 dQ electron t4i cic trung tAm h{p phg cing l6n vi nri nanl itc ch6-in mdn cing cao
TAI LIEU THAM KHAO
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
sep 2003