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 ; 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 M& ddu An mdn kim lo4i ld sg ph6 huli kim lo4i vi hgp kim 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 viQc st dung thu{n lgi vA d6 ddng hon so vdi chcphrrongph6p kh6c V{n d0'd{t lA: phii tim dtrgc ch{t irc chd in mdn c6 hiQu qui nhdt cho ttng lo4i v{t liQu vd tirng mdi trddng cq thd.[Z] lrl0ngqt c0acic phlnt& Blngl Cic 916trining lUlng,nhlfthinhthlnh,momen 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 -'t29356,84 -565776.92 -7382.04 -567240.31 -7217.54 -724995.07 -8194.99 -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 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 10 11 12 13 Trong ddi sdng vi ki thuft, Cu vh hgp kim cfra Cu drrgc srl dgng 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 m6i tnrdng axit hay nu6c tg nhi6n (c6HCO3', CO, , OJ, Cu vi hgp kim cria Cu d6 bi hda tan thirnh Cu2*.MQt sdc6c hrr6ng ad Ur6c phgc sg 6n mdn Cu 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 ning fc chd dn mdn kim lo4i Cu 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 ndng rlc ch6'qu6 trinh in mdn Cu 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 ning rlc chd 6n mdn Cu 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 4.306 -6.402 5.527 -6.083 5.667 -5.946 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 d6:Err*: Ningluong phintfichuabicfri6m obitan thdpnhdt;Ero*:Ninglucrrg obitan thdpnhdt; S:Di€n tichb€mftc0aphdn t01i'y;V:Thdtichprran fi 1i'y 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& 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 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 Blng HlQurudtthYcnghlQm PMntl I I I 10 HQU su{t 55.9 56.8 51.9 65.4 64.9 70.6 763 725 ftci6 u.2 1 12 '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 ning irc chd 6n mdn Cu 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 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 I I 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 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 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 phAn tfch kdt quA ph6p hdi quy dd chi 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 cria cAchydrazon, vh drl do6n khA ning rlc chd 5:nmdn cria mQt sd hydrazon chua dttgc tdng hqp 3.4 Dd doin ning r?c chd in mdn Cu 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 bing 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 4'-OH -0.415 -0.159 -0.111 5.561 5.982808.8889.228 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 mdi trrrdng HNO3 3N '*e-\f-NH-c I |,|,IH, I C*r,*rltV Kdt hgp sdliQu bing vA bing 6, chring tdi nh$n thdv: - HiQu sudt b6o vQ chdng in mdn kim lold r((o)+ (zz)) , P(r)*(s)), vi c6c phAn tir (e)*(zz\ c6 th6m nh6m -CH3hay 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 ndng , CH, , OH), vi nh6m thdNO2 cOdac tfnh 6i electron l6n nhdt rlc chd hydrat h6a m6i trtrdng axit tr6n b6'mat ddng n6n cing lirm giim 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 t