1.

CHNG 1: BN CHT PHN NG N MN

n mn c th nh ngha theo hai cch: -Theo khoa hc n mn: l phn ng ca cht rn vi mi trng -Theo k thut n mn: l phn ng ca kim loi (vt liu) cu trc cng nghip vi mi trng dn n bin i cc tnh cht ca kim loi (vt liu). Qu trnh n mn ca hu ht cc kim loi mang bn cht in ho.Xt phn ng n mn gia Zn v HCl. Phn ng vit nh sau: Zn + HCl = ZnCl2 + H2 Ta vit di dng ion: Zn + 2H+ + 2Cl- = Zn2+ + 2Cl- + H2 hay Zn +2H+ = Zn2+ + H2 (2) (3) (1)

C ngha trong acid H2SO4 phn ng n mn cng c biu din nh phn ng (3). Phn ng (3) c tch thnh hai phn ng Phn ng anode: Phn ng cathode: Zn = Zn2+ + 2e 2H+ + 2e = H2 (4) (5)

Trong phn ng anode, s oxi ha ca km tng t 0 n +2; phn ng cathode s oxi ha ca hydro gim t +1 n 0. V vy tt c cc phn ng n mn u l phn ng in ha. Kim loi n mn th hin bng phn ng: M Mn+ + ne V d: Fe Fe2+ + 2e Ni Ni2+ + 2e Al Al3+ + 3e trng acid. Ngoi ra c cc phn ng kh khc nh: Fe3+ + e Fe2+ Sn4+ + 2e Sn2+ O2 + 4H+ + 4e 2H2O v O2 + 2H2O + 4e 4OH(10) (11) (6) (7) (8) (9)

Phn ng cathode n gin, hay gp nht l phn ng thot hydro trong mi

Phn ng ca oxi ha tan thng gp trong dung dch acid v trung tnh: (12) (13)

i vi mt vi kim loi (st, niken, titan, coban) tc n mn gim trn gi tr th Ep. Kh nng chng li n mn trn vng th Ep c gi l th ng. .

2. CHNG 2: NHIT NG & NG HC N MN KIM LOI 2.1. Nhit ng hc in ho

Nhit ng hc in ho cho php xc nh phn ng t xy ra hay khng tc l khng cn nng lng t bn ngoi. Nhit ng hc l c s cho cc php o in ho tin hnh trong k thut n mn.

2.2. Quan h G v E
Mi qu trnh t din ra u c bin thin nng lng t do Gibbs m. Trong in ho, G lin quan n nng lng in tch khi chuyn qua b mt phn chia pha kim loi/dung dch theo biu thc: G = -nFE G l bin thin nng lng t do, n l s electron tham gia phn ng, E l chnh lch in th thun nghch (electron chuyn qua b mt phn chia pha). Nng lng cn chuyn mt lng in tch nF mt cch thun nghch khi c chnh lch in th E. Nu bin thin nng lng l m, khng cn nng lng t bn ngoi, phn ng s t xy ra.

2.3. in cc so snh SHE v cc loi khc

in cc so snh hydro gm: mt mu Pt nhng trong dung dch acid c hot bng 1. Bng kh hydro sch thi vo v thit lp trng thi kh hydro tiu chun P=1 atm. in cc so snh hydro ni vi mt na pin khc thng qua cu ni mui c tm ngn bng thy tinh xp, ch cho php chuyn in tch, khng cho chuyn cht. Th in cc EPt3+/Pt cho ha tan Pt l +1,2V rt dng hn so vi E H+/H2. Pt ch ha tan th rt dng, xa vi th kh ca phn ng 2H + + 2e = H2, Pt khng ha tan, ch l cht xc tc cho phn ng ny hnh thnh trn b mt. Tn in cc Hg-HgSO4 Cu CuSO4 Calomen bo ha Phn ng HgSO4 + 2e =2Hg + SO42EHg/HgSO4 = 0,615 0,0295log(SO42-) CuSO4 + 2e = Cu + SO42ECu2+/Cu = 0,340 - 0,0295log(Cu2+) Hg2Cl2 + 2e = 2Hg + 2ClTh V (SHE) +0,615 +0,318 +0,241 2

Ecal. = 0,268 - 0,059log(Cl-) AgCl + e = Ag+ + ClAg-AgCl bo ha Hydro tiu chun EAg/AgCl = 0,222 + 0,059pH ( thay Cl- bng H+) 2H+ + 2e = H2 +0,222 0,0

2.4. Phng trnh Nernst

Tnh cht nhit ng ca cc phn ng in ho ph thuc: nng cc cht tham gia phn ng, nhit . Phng trnh Nernst m t mi quan h ny.

in th thun nghch c tnh

E: in th thun nghch, E0: in th thun nghch tiu chun, Ox: cht oxi ho, Rd: cht kh.

2.5. ng hc qu trnh n mn in ha
2.5.1. nh lut Faraday : Phn ng in ha to ra hoc tiu th electron . V vy tc ca dng electron n hay i khi vng tip gip din ra phn ng c xem l tc phn ng. Dng electron o bng dng in (ampe). Mt ampe tng ng 6,2.10 8 electron /giy. nh lut c th hin : m =
I .t.a n .F

F l hng s Faraday; n : s ng lng trao i; a : khi lng nguyn t; t l thi gian. m l khi lng cht sinh ra hoc mt i. nh lut c biu din cch khc: r =
m t.A

i.a n .F

Vi i l mt dng in v bng I/A. Biu thc cho thy mt dng n mn t l vi tc n mn, cng mt dng in tp trung vo din tch nh hn s c tc n mn ln hn. 2.5.2. Mt dng trao i Xt phn ng : 2H+ + 2e = H2 Ti th oxi ha kh hay th in cc n tiu chun E o H+/H2, phn ng t trng thi cn bng th tc phn ng thun bng tc phn ng nghch, lc ny: 3

r thun = r nghch =

i o .a n.F

io l mt dng in trao i (Exchange Current Density) ti cn bng. Bn cht b mt nh hng ln n mt dng in trao i. B mt trn din ra phn ng khng nh hng n th in cc, ngc li i o b nh hng kh mnh ca b mt. Hay ni cch khc G khng b nh hng bi tnh cht b mt nhng khi i o th rt nhy vi cc tnh cht ca b mt. V d: Mt dng trao i io ca phn ng (3) trn thy ngn l 10-12 A/cm2 nhng trn Pt th cao gp 9 ln ( 10-3 A/cm2).io c tnh trn c s cu trc hnh hc ca b mt. Vi in cc Pt ph mui Pt s c io ln do din tch ln hn (xp). 2.5.3. Phn cc Phn cc l s dch chuyn in th in cc (E Ecb) khi th cn bng Ecb - gy ra do phn ng tng trn b mt i vi cc phn ng n. Phn cc cathode c : cc electron cp n b mt do phn ng chm v gy nn in th b mt E m hn e. Do vy c c xc nh l m. Phn cc anode : electron ly ra khi b mt, s thiu ht electron gy ra s thay i in th. in th chuyn v pha dng hn, do vy a dng. C hai dng phn cc quan tm: phn cc hot ha (activation) v phn cc nng (concentration). Phn cc hot ha Khi mt giai on no ca phn ng chm s khng ch tc dng electron ,lc ny ta ni phn ng b khng ch bi s chuyn in tch v gy ra s phn cc hot ha. Xt phn ng : 2H+ + 2e = H2 Trn b mt s c ba giai on: - H+ phn ng vi electron trn b mt kim loi, hnh thnh Hh.ph trn b mt. H+ + e =H h.ph Hai Hh.ph phn ng vi nhau to H2 Hh.ph + H h.ph = H2 -Cc phn t lin kt vi nhau li thnh bng kh hydro trn b mt kim loi.

Mi quan h gia phn cc hot ha hay qu th v tc phn ng c trng bi ia, ic. a = a log
ia ic ; c = c log io io

i vi qu th anode, a l dng do vy a dng. Tng t cho qu th cathode, c m v c m. a, c l cc hng s Tafel cho cc phn ng n. Tc c o bng ia hay ic tng theo s thay i ca qu th. Gi tr tuyt i ca hng s Tafel nm trong khong 0,03 0,2 V v c th khng bng nhau nh gi thit. Xt phn ng 2H+ + 2e = H2 Phn ng t cn bng ti EH+/H2, lc ny tc phn ng thun bng tc phn ng nghch. Nng lng t do tng ng c th hin trn hnh. G*thun , G*nghch tng ng l barier nng lng ca phn ng thun, nghch. bin thin nng lng t do quan h vi th in cc: G*thun - G*nghch = GH+/H2 rnghch l hm ca nng lng hot ha. rthun = Kt. exp(= -nFeH+/H2

Theo nh lut phn b Maxwell v nng lng ca cc ht phn ng: r thun v

G * thun RT

rnghch

= Kn. exp(-

G * nghch RT
i o .a nF

Kt, Kn l cc hng s phn ng cho phn ng thun v nghch. Ti gi tr cn bng: rthun = r nghch =

io = Kt. exp(-

G * thun RT

) = Kn. exp(-

G * nghch RT

R rng io l mt hm ca nng lng hot ha. Khi phn cc cathode hay c qu th c trn b mt in cc, tc phn ng phng in gim v qu trnh ion ha tng ln. iu ny c c bng vic gim nng lng hot ha cho phn ng phng in mt lng nng lng nFc v tng cho phn ng ion ha mt lng (1)nFc.Tha s v 1- l t l ca c tham gia vo phn ng phng in v ion ha. Tc phng in cathode v anode s tr thnh: 5

ic =

Kt

. exp(-

G * thunnFc RT

Kn. exp(-

G * nghch +(1 )nFc RT

Khi phn ng cathode xy ra thun li, dng tng s l: itng.c = ic - ia = io .exp(

(1 )nFc nFc ) - io . exp( ) RT RT

Khi phn ng anode thun li ( ion ha thnh H+ thun li) itng.a = ia - ic = io .exp(
(1 ) nFc nFa ) ) - io . exp( RT RT

l phn ca a mt i bi phn ng ion ha anode (phng trnh ButlerVolmer) n gin li: itng.c = ic - ia = io. exp( khi c cao v hot ha, c = c log(ic/io) Khi a cao: hot ha,a = a . log (ia/io)
nFc ) RT

vi c =

2,3RT nF

2.6. o ng cong phn cc vi h ghp ni galvanic d on n mn

n mn galvanic din ra khi hai kim loi c tip xc in v bng ion, nh hnh di

V d in hnh ca h ny l anode hy sinh km trong nc bin, Mg trong nc sinh hot bo v thp.

Xem xt ng cong phn cc sau ca hai kim loi. Kim loi 1 bn hn (E corr dng hn), c mt dng n mn thp hn. Nu din tch b mt in cc l ging nhau, th b mt tip xc kim loi-dung dch ca hai kim loi ny s i n mt gi tr bng nhau. Lc ny Ti im ct ca dng tng anode v dng tng cathode E couple l th o c khi hai kim loi tip xc in vi nhau trong mi trng n mn. Th Ecorr ca kim loi 1 chuyn v pha m hn, dn n tc n mn nh hn. Kim loi 2, chuyn th n mn v pha dng hn, tc n mn tng ln. i couple s dng tnh tng ca tc n mn ca kim loi 2. Do c ni vi kim loi 1 nn tc ho tan tng t i corr 2 n icouple. Ngoi ra, gim tc ho tan kim loi 1 c th xc nh bng ngoi suy ng anode ca kim loi 1 n Ecouple. Vi ni ghp ny, kim loi 2 b ho tan gim tc ho tan ca kim loi 1.

3. CHNG 3 : CC PHNG PHP BO V KIM LOI A. BO V CATHODE 3.1. Gii thiu chung
L phng php tt nht trong cc phng php in ho bo v kim loi, c th khng ch hon ton qu trnh n mn. L phng php bo v kim loi quan trng v linh hot. Nm 1824 Davy Hamphrey ng mt lot bi bo vi Hip hi Hong gia Anh quc v kh nng s dng in cc anode Fe, Zn bo v cho lp ph bng Cu thn tu bin hi qun. Lp Cu c bo v rt tt. Tuy nhin, thiu ion Cu, to iu kin cc sinh vt bin pht trin, thn tu nhiu bm bn, mt v p bn ngoi. Vic bo v n mn Cu tr nn khng cn thit bng vic chng tc hi ca cc sinh vt bin. Phng php i vo qun lng. Phi n 100 nm sau, phng php ny tr nn c hiu qu khi s dng bo v h thng ng dn du ngm di t ca cc cng ty du kh M.

3.2. Nguyn tc
Trong mi trng n mn c nc, phn ng ca Fe vi khng kh c vit 2 Fe + O2 + 2 H2O 2 Fe(OH)2 Sn phm st hydroxit tip tc oxi ho to thnh st t (Fe 3O4) hay FeOOH (r st). Nu tch lm hai phn ng 2 Fe 2 Fe2+ + 4 eO2 + 2 H2O + 4 e- 4OHV bn cht, n mn l mt phn ng in ho, c cht cho v cht nhn electron. Phn ng anode cung cp electron, phn ng cathode nhn electron. Tuy nhin, thc t mi kim loi c mt hoc nhiu th in cc, do vy, in th o c l in th hn hp hay in th n mn Ecorr. Nu ly electron ca phn ng 2 cp cho phn ng 3, tc phn ng 2 s tng nhanh, phn ng 3 s chm li. Ngc li, nu cp thm electron trn b mt kim loi, phn ng cathode s nhanh ln, phn ng anode s b c ch chm li. y l nguyn l c bn ca phng php bo v cathode.

Hnh trn, ng cong phn cc c trng cho qu trnh n mn v bo v cathode.

Khi phn ng cathode b khng ch bi qu trnh chuyn cht, dng ng cong phn cc nh hnh trn.

3.3. Phn ng kh ca oxy

Trong qu trnh n mn, nu cc cht phn ng cathode c cung cp y , tc ca phn ng cathode b khng ch bi qu trnh chuyn in tch qua b mt. Do oxy tan hn ch trong nc (khong 10 ppm trong nc bin lnh), lng oxy trn b mt kim loi rt nh. Phn ng cathode b quyt nh bi tc khuch tn ca oxy n b mt qu trnh chuyn cht quyt nh tc phn ng. Nu phn ng cathode xy ra rt nhanh, nng oxy s gim n 0 (c ngha oxy tiu th trn in cc nhanh hn chuyn n), tc phn ng cathode t gi tr ti hn.

3.4. Gii phng H2

V nguyn tc, nc cng c th l tham gia phn ng kh 2 H2O + 2 e- H2 + 2 OHThc ra, trong mi trng nc, n mn st vi kh H 2 thot ra do phn ng kh l thun li v mt nhit ng hc. Nhng phn ng kh ny khng c nh hng ln do phn ng kh ca oxy thun li c nhit ng hc v ng hc. Khi thiu oxy, phn ng thot H2 ti th n mn ca st chm, tc n mn rt nh. Mt d phn ng thot H2 chim phn nh khi thp b n mn trong mi trng trung tnh, nhng ng k khi th h thp n th bo v cathode. Trn hnh di, khi p dng ngoi ti bt k th no cng phi duy tr dng cathode tng, c ngha c hai phn ng cathode kh O2 v thot H2.

C hai phng php nguyn tc trong vic phng php bo v cathode: k thut p dng ngoi v s dng anode hy sinh.

3.5. Phng php anode hy sinh

3.5.1. Nguyn tc 10

K thut ny to ra ng lc cho qu trnh bo v bng s chnh lch th ca vt c bo v vi mt kim loi khc cng trong mi trng. Khng c ngun ngoi p t vo. Kim loi khc ny s ho tan cung cp electron phn cc cho vt cn bo v. Kim loi ny phi c in th m hn kim loi trong vt cn bo v trong mi trng . Do vy, Zn, Al, Mg c th bo v cho thp, st bo v cho Cu. Bng di, p dng anode hy sinh trong bo v cathode.

Khi electron cung cp cho tip xc kim loi/dung dch, tc phn ng cathode tng, tc phn ng anode gim. V vy n mn gim. n mn s ngn cn hon ton khi tc cp electron phn ng anode khng xy ra. Khi hai kim loi c in th khc nhau, nhng trong dung dch. Nu c ni vi nhau bng dy dn in, chng s c khuynh hng phn cc ho ln nhau. Dng ion chuyn trong dung dch, dng electron chuyn t anode sang cathode qua dy dn. Khi cung cp electron cho cathode, anode b tiu hao nhanh hn, v vy c gi l anode hy sinh. Phng php anode hy sinh c p dng: thn tu, gin khoang du kh, h thng ng dn di t, di nc, cc cng trnh ngm, cc b mt kim loi thng 11

xuyn tip xc vi mi trng n mn nh thit b trao i nhit, bm piston, cc loi v o . . . . 3.5.2. Hot ng Th hot ng ca vt liu lm anode l th m khi c ni vi vt liu bo v. Thc t, do cc anode thng mi c sn xut c th hot ng khi b phn cc mt t nn th hot ng s tng ng vi th h mch. Th bo v l th m ti n mn kim loi b dng li. Cc vt liu khc nhau, th bo v cng khc nhau (bng di)

3.5.3. Kh nng v hiu qu ca anode Kh nng ca anode l tng in tch coulomb (dng x thi gian) sn sinh ra trong mt n v khi lng ca anode khi b ho tan in ho. Thng c biu din A.h/kg. V l thuyt, dung lng (kh nng) ca anode c tnh theo nh lut Faraday. V d 1kg Al c th to ra mt in lng 2981 Ah. Gi tr thc t th nh hn. Dung lng anode thay i theo loi vt liu. Hiu qu anode c tnh:

Hiu qu anode thng khng my ngha thc t, c th b qua. V d, hiu qu c hp kim Mg thng t khong 50% trong khi hp kim Zn vt qu 90%. Khng c ngha rng anode hp kim nhm tt hn hp kim Mg. 3.5.4. Yu cu ca anode -Vt liu anode phi to ra mt th, dng ln phn cc cathode c hiu qu. Anode c th hot ng m hn th ca vt cn bo v. -Vt liu anode n nh trong khong th hot ng. Do vy, anode chng li c s phn cc khi c dng.

12

-Anode c dung lng cao, n nh, c th cung cp nhiu A.h trn mt kg vt liu b tiu hao. Vt liu khng b th ng trong mi trng, mn u trnh v tng mnh v s gn t c dung lng l thuyt. -Cc anode l hp kim cn c cc tnh cht c hc cn thit, thc t, hp l v gi c. 3.5.5. Vt liu ch to anode hy sinh Trong h thng bo v cathode, anode hy sinh phi c in th m hn so vi vt bo v. bo v thp C, cc kim loi hay s dng l Mg, Al, Zn. cc kim loi K, Na, Li tuy c th m hn thp nhiu nhng b n mn nhanh trong mi trng nc. Thc t, cc kim loi nguyn cht khng s dng lm anode hy sinh do khng tho mn c cc iu kin trn. Bng 10.7, lit k cc vt liu anode quan trng, km cc tham s hot ng. Hp kim Mg c th hot ng rt m, nn bo v cathode vi th ng (driving voltage) ln. Zn v hp kim Al l ph bin nht. Hp kim nhm c kh nng duy tr dng n nh gp i hp kim Zn v Mg. Trong khi ch to hp kim, c th thm cc cht khc ci thin tnh cht ca vt liu anode. Rt cn thit kim tra lng tp cht trong anode, cc tp cht ny nh hng nhiu n hot ng ca anode.

Bng 10.8 ch ra cc yu cu v cht lng ca kim loi chnh ph trong 3 loi anode thng thng.

3.6. K thut p dng ngoi

3.6.1. Nguyn tc hot ng Nguyn tc hot ng th hin hnh di. Mch bao gm: ngun in, dung dch n mn, vt bo v. Vt c bo v s b phn cc cathode. C vt bo v v in cc p dng phi tip xc trong dung dch in ly.

13

Ngun in c ly t chnh lu. Khong th 15-100V, dng 5-100A. in cc p dng l anode. Anode c cc loi: anode b n mn, anode tr, anode bn n mn (semi-consumable). Trong mi trng n mn (cht in ly) cc ion OH -, Na+ . . . vn chuyn, kn mch in. Tiu thu anode khong 9kg/A.nm. Do vy in cc anode b n mn ny thng phi thay th. iu quan trong hn l rt kh m bo ni in c lin tc khi anoe b n mn. Vi cc anode tr (lm bng Ti m Pt) , phn ng trn in cc l 2 H2O O2 + 4 H+ + 4 eHay khi c Cl2 Cl- Cl2 + 2 e-

in cc loi ny t thay th, bn vi cc sn phm anode, mt dng lm vic cao, nhng to ra acide cao (pH<2) v, lng kh nhiu. Vi cc kt cu ngm, s gp kh khn. Tuy nhin, lp ph Pt mt mt khong 2,5 -10 m. Ch yu do mi mn c hc.

14

Loi bn ho tan, tan t hn so vi tnh theo nh lut Faraday, so vi in cc anode tan (n mn). C c iu ny l do phn ng anode b chia s oxi ho vt liu v oxi ho mi trng. in cc thng lm bng Si-Fe, Cr-Si-Fe, graphite. Thc t, kim loi nguyn cht khng s dng lm anode hy sinh bi cc l do sau: -Anode cn n nh, tin cy, hot ng th m -Dung lng cao (Ah/kg) -Ho tan ng u, hiu sut s dng cao khi cp dng cathode -Khng b th ng Vi cc yu cu ny, hp kim thng s dng lm cc anode thng phm. 3.6.2. Yu cu v dng in Dng cathode thay i ph thuc vo mi trng n mn. y l l do la chn p dng tt nht phng php bo v cathode trong mi trng gn trung tnh. Khi acid cao, yu cu dng ra cao, khng kinh t. Mi trng kim, t n mn vt bo v v thng khng thc hp. Bng di, th hin mt s mt dng c tnh vi bo v cathode.

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3.7. Thit k h thng bo v cathode

Khi thit k h thng bo v cathode bng anode hy sinh kho st cc yu t sau: -Din tch chi tit cn bo v -Nu c th loi lp ph no c s dng -Mt dng cathode -Thi gian lm vic ca h bo v 3.7.1. Din tch bo v tnh tt c din tch tip xc vi cht in ly ca chi tit. Thc t, c th gi thit l din tch phng, khng g gh. Nhiu chi tit c ph bn ngoi. Din tch bo v c tnh vi cc din tch khng c ph, din tch khng lm vic trong lp ph. Thc th, gi s mc lp ph b hng (%) t tnh c din tch cn bo v cathode

Din tch hng (breakdown) s thay i theo thi gian lm vic ca chi tit, do din tch cn bo v s thay i.

Bng trn th hin % lp ph b hng theo thi gian. 3.7.2. Mt dng cathode bo v thp

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Gi s mt dng cn bo v thp (ly th ca thp l -0,8 v Ag/AgCl/nc bin) cho cc bng trn (10.13; 10.14). Ch rng, dng yu cu cho chi tit s dao ng theo nhit , mc thng kh, dng chy, phm v bo v, trng thi chn lp, cc loi vi khun, mui. iu quan trng l mt dng cn bo v phi tnh chnh xc. Nu qua cao, s lng ph, qu thp th chi tit khng bo v c.

3.7.3. Thi gian lm vic ca h thng bo v Thi gian lm vic ca h thng c th n 40 nm. Thi gian lm vic cng di, tiu tn anode cng ln. Thi gian lm vic khng lin tc, cc iu kin lm vic cng phi xem xt n. Cc thng cha hay phao thng bng cho thuyn c khi nhng chm tt c, c khi mt na, c khi khng lm vic. Ngoi ra, din tch t ca thn tu ph thuc vo thu triu, iu kin ma. 3.7.4. Tnh ton khi lng, s lng anode 17

Khi lng anode bo v trong thi gian lm vic c tnh

W = iav . A.l.8760 C

W: Tng khi lng anode (kg); A: din tch chi tit cn bo v (m2), iav: mt dng yu cu cho chi tit; l: thi gian lm vic ca h thng bo v (1 nm = 8760 gi); C l dung lng ca anode (Ah/kg). D nhin, tng khi lng anode phi ln hn hoc bng khi lng W tnh trn. Anode phi cung cp dng bo v t khi bt u n khi kt thc. V hnh dng ca anode, thc t khng c kch thc tiu chun. C th la chn cho ph hp vi kch thc chi tit. Dng ra ca anode ph thuc vo din tch b mt. Ni chung, anode ln s c dng cao. Anode c cng khi lng nhng khc nhau v kch thc c th khc nhau dng ra. V vy, vi mt khi lng ca anode, hnh dng s phi mt chng mc no khi xem xt dng ra. 3.7.5. Dng ra anode L dng lun sn c t anode trong iu kin lm vic. Dng s ph thuc vo hnh dng anode, in tr ca mi trng, th bo v ca chi tit v th hot ng ca anode. Dng c xc nh
I= ( E 2 E1 ) R

Vi I: dng ra (A); E1: th hot ng ca anode (V); E2: th bo v (V); R: in tr anode (Ohm). Th bo v ca thp trong mi trng thng kh l -0,8 V (Ag/AgCl/nc bin). 3.7.6. in tr anode Bng di y lit k cc gi tr in tr R ca anode trong iu kin anode nhng chm. Cc cng thc tng t vi trng hp chn ngm.

18

 tnh ton in tr anode, cn c thng tin v tr ca mi trng. Vi ng nhng chm, in tr ca nc c th tnh theo th sau.

3.7.7. Thi gian lm vic ca anode C th tnh theo cng thc sau:
L= MU IE

Vi L: thi gian lm vic thc ca anode (nm); M: khi lng ca anode n (kg); U: tha s s dng ( 0,75 0,8 i vi anode b ); E: tc tiu th anode (kg/A.nm); I: dng ra anode (A). U l mt hm ca hnh dng v phn vt liu anode

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tiu th phn cn li khng th cung cp dng theo yu cu. Ko di thi gian lm vic ca anode khng c li. 3.7.8. S lng anode S lng anode cn c N c tnh nh sau: N =
A.i av I

Ch NxM phi bng hoc ln hn tng khi lng W theo yu cu. Thc t, rt kh c c chnh xc dng ra v khi lng ca vt liu anode ng thi. Do vy, phi chp nhn mt sai s no y nhng t nht phi ng vi yu cu thit k. Cn phi kim tra anode c cung cp dng cho chi tit bo v khng. Thc t, dng ra tnh ton theo lng 90% anode tiu thu. 3.7.9. Phn b anode R rng, mt lng ln anode phn b khp chi tit s ci thin phn b dng bo v tt. Nhng khng th vt qu s anode theo tnh ton. Kch thc anode phi m bo thi gian lm vic theo thit k. Qu nhiu anode, khi lng ln s khng c hiu qu kinh t. Rt cn thit phi phn b ton b chi tit c bo v, c bit quan trng v d nh cc anode chi tit ngoi bin. Phi trnh qu bo v. Do vy, anode hy sinh cn phn b m bo th bo v phn b u trn chi tit. Mc dao ng ca t l dng ra / khi lng c th chp nhn bng cch thay i hnh dng. Tng phn b dng l ht sc cn thit. Anode gn chi tit l ht sc quan trng. V d nu anode hy sinh t trn hoc rt gn ng dn trong t, dng ra t b mt anode gn vi cc cng trnh thp s b gii hn rt nhiu. Hay mt v d khc, mi trng c dn cao, sn phm n mn s lp y khon cch anode n chi tit. Anode d b chn ng gy h hng. Khi t anode qu xa, mt phn chnh lch th tiu hao do phi khc phc tr gia anode v cathode. 3.7.10. Gn anode Anode cn gn chc chn bm cht vo chi tit v phi hn hay lin kt c kh vi cathode. Anode c th gn nm ngang, ng. Phng php gn anode vo b mt ng hay chi tit nhng chm kh phc tp. Hnh di m t cch ghp

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Hnh e, ng ph btng vi anode gn cht, chiu dy anode bng chiu dy btng.

B. BO V ANODE
Theo Fontana v Greene, bo v anode l mt trong nhng phng php ngha nht trong lch s khoa hc n mn. Bo v anode c m t nh mt phng php gim tc n mn bng cch to lp ph th ng. V vy, ch p dng vi cc kim loi v hp kim c th th ng khi tip xc vi mt dung dch thch hp. Do vy, s gim n mn, tng tui th ca chi tit, mang li hiu qu kinh t, c ngha trong vic bo qun, vn chuyn ho cht. Edeleanu ln u tin dng dung dch acid bo v anode th nghim trn ni hi bng thp khng r quy m nh. c xem l ng dng u tin trong cng nghip.

3.8. Nguyn tc
Chng ta hy so snh hai phng php bo v cathode v anode. C hai k thut ny dng gim tc n mn trong dung dch in ly, ph thuc vo c ch in ho ca kim loi khi tip xc vi dung dch in ly, lm thay i th ca kim loi. Trn gin th-pH trong h Fe-H 2O ch ra ln v xu hng thay i ca in th khi Fe nhng trong nc (pH=7) cn phi lm cho n th ng hoc khng ho tan.

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Nu th ng, bn ca kim loi ph thuc vo s hnh thnh lp bo v trn kim loi, bn nhit ng hc, kim loi uc bo v. Mt khc bit ln trong bo v anode l tc n mn lun c xc nh, trong khi , bo v cathode, kim loi khng b n mn. Khi tng th bo v, kim loi c th tng tc n mn nu kim loi ri vo trang thi qu th ng, y th kim loi di th bo v s khng nh hng n tc n mn tuy nhin tiu hao nhiu nng lng. Tuy nhin th qu m, trong mt s trng hp li khng tt. V vy, qu hoc di bo v c th tng tc n mn. Palmer cho rng, th ng l rt khn ngoan. Trong bo v anode, chi tit cn bo v l anode, cathode thch hp nh thp thp C, khng r, hay graphite. Th ca anode duy tr trong min th ng bng potentiostat vi in cc so snh thch hp.

3.9. Th ng kim loi

Bo v anode lin quan n s th ng ca kim loi. Xu hng th ng ph thuc vo c kim loi v cht in ly. Kh nng th ng tng khi mt dng uy tr th ng (ipass) gim, in tr tng ca mng tng. Th th ng cng thp, th ng cng n nh.

Gi tr ca th Flade EF (V) c tnh: Ti -0,24; Cr -0,22, thp +0,1; Ni +0,36 v st l +0,58. Cc gi tr ny ch tng i v n ph thuc vo iu kin th nghim nh pH ca dung dch. Cng thc th Flade

0 EF th Flade tiu chun ti pH=0; n l s trong khong 1 2 ph thuc kim

loi v iu kin ca n. Bng 10.30, cho cc gi tr mt dng duy tr th ng ca kim loi c th v in tr tng ca mng. Nhng kim loi c th Flade thp hn NHE (0 ti a H+ =1) 22

c th b th ng bng cc acide khng oxi ho. C ngha, Ti b th ng do cc ion H+ c mc oxi ho , trong khi , thp cn tc nhn oxi ho mnh nh HNO 3 m c. Kim loi th ng nhiu hay t thng s d th ng v thp th Flade, nh hp kim ca Fe v Cr trong 10% trng lng H2SO4 (bng di)

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Cc thng s ny ph thuc thnh phn, nng , tinh khit, nhit v s khuy trn dung dch. Mt dng cn t c v duy tr th ng i pass trong nhiu mi trng cho bng 10.33. C th thy, thp ny d th ng hn 100000 ln khi ngm trong H3PO4 115% hn trong 20% NaOH. Nng cht in ly cng ht sc quan trng (bng 10.34). C mt cc tp cht, c bit cc halogien, s ph mng th ng. Tng nhit , s c nhng nh hng:kh to mng th ng, gim vng th th ng v tng mt dng hay tc n mn trong qu trnh th ng (hnh 10.54 l thp trong 10% H2SO4). Khi bo qun acid, nhit bn ngoi thay i theo ma, c th tng gp i dng yu cu bo v.

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Khuy trn c th tng tc n mn ca kim loi nhng chm v tng mt dng dng th ng (bng 10.36).

C. BO V BNG LP PH BIN TNH 3.10. Oxi ha nhum mu nhm

bo v nhm v hp kim nhm, ngi ta to trn b mt n mt lp oxit bng phng php ho hc hoc in ha. Mng oxit dy hoc mng theo iu kin oxi ho. Mng c th dy n hng trm m. Mng c rn cao, c kh nng hp th mu, thm du m tt nn c th lm vic ni c ma st cao. Sau khi oxi ho, mng c em i nhum mu v c hoc hu c. 3.10.1. Phng php ha hc Phng php ny to bn ca mng khng cao, t s dng. Thnh phn dung dch oxi ha nh sau: Na2CO3 : 50g/l ; NaOH Thi gian : 5 30 pht 3.10.2. Phng php in ha C cu mng oxit 25 : 2 2,5 g/l; Na2CrO4 : 15 g/l;

Mng c hai lp: lp mng, st cht st b mt Al. Cu to t oxit nhm ngm nc, chiu dy 0,01 0,1m. Lp bn ngoi ngm nc nhiu hn. Khi nhng nhm vo dung dch, anode nhm c qu trnh ha tan in ha nhm Al = Al3+ + 3e ng thi nhm tc dng vi dch in phn theo phn ng 2Al + 3H2SO4 = Al2(SO4)3 + 3H2 Din ra ng thi vi qu trnh ha tan nhm l qu trnh thot oxi theo phn ng 4OH- - 4e = O2 + 2H2O Qu trnh gii phng oxi c th qua cc bc: 2OH- = H2O + O - O2- = O - + e O= O + e 2O = O2 Cc sn phm trung gian O2-, O tc dng vi nhm anode (vt cn oxi ha) 2Al3+ + 3O2- = Al2O3 2Al + 3O = Al2O3 Qu trnh hnh thnh mng nhanh chng, mng to c st, mng chiu dy hu nh khng thay i trong sut thi gian oxi ha. Qu trnh ha tan mng s xy ra ng thi: Al2O3 + 3H2SO4 = Al2(SO4)3 + H2O H+ + 2e = H2 Khi hnh thnh l xp: O2-, O khuych tn qua mng y cc l xp v hnh thnh Al2O3. Phn ny s tip tc pht trin lm dy thm mng oxt. ng thi phn mng pha trn s b ha tan do vy chiu dy mng hu nh khng i, phn trn cc l xp c dng hnh cn. Trong cc l xp c cc phn ng hydrat ha Al2O3 + H2O = Al2O3.H2O Al2O3 + 3H2O = Al2O3.3H2O Al2O3.nH2O + H2SO4 = Al2(SO4)3 + (n+3) H2O 3.10.3. Dung dch v ch in phn : H2SO4 : 180 200g/l; nhit : phng; mt dng anode Da:1,5 2 A/dm2 26 Ha tan mng ny s to ra cc l xp. cathode, qu trnh kh :

Thi gian oxi ha : 40 50 pht 3.10.4. Nhum mu nhm Mng Al2O3 xp nn c kh nng hp ph cc cht mu hu c. i khi cc cht mu tc dng vi mng oxt to cc hp cht ha hc. Cc cht mu v c hnh thnh do cc phn ng to cht mu. V d: nhum vng da cam nhm c tin hnh nh sau: -X l b mt nhm trc khi oxi ha -oxi ha in ha nhm trong acid, ri nhng vo dung dch K2Cr2O4 trong 30 pht. Sau li nhng vo dung dch AgNO3. Mu vng da cam c c do phn ng: 2AgNO3 + K2Cr2O4 = Ag2CrO4 Thnh phn g/l 10 100 40 100 100 200 10 50 + 2KNO3 Ag2CrO4 kt ta mu vng da cam. Thnh phn dung dch nhum mu Mu Nu en Vng Vng nht Dung dch 1 CuSO4 Pb(CH3COO)2 Pb(CH3COO)2 Pb(CH3COO)2 Dung dch 2 K4Fe(CN)6 KMnO4 K2Cr2O7 Na2SO4
Thnh phn

(g/l) 10 50 15 25 50 100 10 50

Hp cht mu Cu2 Fe(CN)6 CoO PbCr2O7 PbSO4

Cc mu sau khi nhum mu phi sy kh. Cht hu c hay s dng l Alizarin t 2 5 g/l, nhum nhit 50 60oC. Mu ph thuc thi gian ngm mu. 3.10.5. Pht pht ha kim loi Pht pht ha (PPH) l qu trnh to mng bo v trn b mt chi tit. Mng gm cc mui pht pht ca Fe, Mn, Zn hay hn hp cc mui ny. Mng PP c bn khng cao do xp, nn bn n mn km. Nhng li c kh nng hp ph tt nn lm nn sn hoc gia cng thm trong dung dch cromat ri thm du bt kn cc l xp s tng bn n mn. Mng PPH r tin, to nn tt cho sn. Tnh bo v ca mng PP ph thuc: nng mui PP trong dung dch, thi gian, thnh phn thp v trng thi b mt trc khi PP. Lp PP tan trong nc 25oC l 1,5mg/l; 90oC l 10,6g/l; tan mnh trong acid v kim. 3.10.6. Pht pht ho nng Chia lm hai loi: PPH thng v PP nhanh -PPH thng

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Nhng mu thp vo dung dch mui PP dng ha tan nh km, mangan, thng dng l mui Majep (hn hp mui st va Mn pht pht) hay dng mono photphat Me(H2PO4)2 nhit thng, c phn hy nhng khng ng k: Me(H2PO4)2 = MeHPO4 + H3PO4 Khi un nng: 5Me(H2PO4)2 = 2MeHPO4 + Me3(PO4)2 + H3PO4 Nhng thp vo dung dich pht pht ho xy ra 2 qu trnh: Anode : Fe = Fe2+ + 2e Cathode 2H+ + 2e = H2 Ion H+ do s phn ly ca H3HPO4 t do hay do: Me(H2PO4)2 = Me2+ + 2H2PO4H2PO4- = H+ + HPO42HPO42- = H+ + PO43Kt qu l lp dung dch gn b mt mu thp giu ion Fe 2+ cng nh HPO42- ; PO43- ; Fe3(PO4)2 ; Mn3(PO4)2. Bi vy lp dung dch y t qu bo ho v kt tinh ln b mt thp tho thnh lp ph pht pht: Fe2+ + HPO42- = FeHPO4 Mn2+ + HPO42- = MnHPO4 Zn2+ + HPO42- = ZnHPO4 Hay 3Fe2+ + 2PO43- = Fe3(PO4)2 3Mn2+ + 2PO43- = Mn3(PO4)2 3Zn2+ + 2PO42- = Zn2(PO4)2 Nhit cao th mui monophtpht d phn hu do MeHPO 4 v Me3(PO4)2 c th kt ta trn b mt thp v ngay c trong dung dch. Nu khng ch nhit thp th thi gian PPH ko di. Thi gian PPH ph thuc: Thnh phn kim loi, phng php gia cng b mt trc khi PPH, y s axt chung v axt t do, nhit . Thnh phn v ch PPH [nFe(H2PO4)2.[mMn(H2PO4)2]: 30 - 35 g/l Nhit : 97 99oC Thi gian : 40 - 80 pht -PPH nhanh 28

 tng tc PPH kim loi en, thng thm vo dung dch PPH cht kh hay cht hu c. Thi gian PPH gim cn 10 15 pht Cc cht thm vo l cht kh phn cc, thc y qu trnh cathdode. Cht oxi ho thng dng l mui nitrit, nitrat. Cht kh l mui bisulphit, sulphit.. Cht hu c nitrobenzen; hydroxylamin; thioure. Thnh phn (g/l): [Fe(H2PO4)2][Mn(H2PO4)2]: 30 Zn(NO3)2.6H2O : 60 Nhit : 92 - 96 oC Dung dch khc Zn(H2PO4)3.2H2O : 35 37 H3PO4 t do : 15 - 16 Nhit : 85 - 95oC 3.10.7. Pht pht ho lnh Tin hnh nhit thng, khng cn khng ch nhit nghim. Mng PPH mng dng lm lp lt cho sn. Trong dung dch c cc cht lm tng nhanh tc ho tan kim loi nh Zn(NO3)2; KClO3 ; NaF. Thnh phn (g/l): Dung dch 1 : H3PO4 t do : 80 85 pH: 2,7 - 3,1 3.10.8. Cromat ho b mt kim loi Lp cromat ca cc b mt kim loi Al, Mg, Zn, Cd, Sn, Cu, Ag bm tt, bn n mn. Mu sc: xanh lam, vng, xanh lc, en l nhng hp cht Cr 3+ c mt Cr6+. Kh nng chng n mn ca lp cromat khng phi do s th ng b mt kim loi m khi c mt cromat lm mt tc dng ca m mi trng. Hm lng cromat trong lp b mt cng cao, chiu day cng dy, bn n mn cao. Cng mu ca lp cromat ph thuc t l Cr3+/Cr6+. Phng php cromat ho gm hai giai on: +X l b mt kim loi + Nhum mu trong dung dch c ca axit cromic v H2SO4. Sau nhum xanh trong dung dch kim. 29 ZnO : 15 17 NaNO2 : 1 2 Thi gian : 15 20 pht Zn(NO3)2.6H2O : 52- 53 T l axit chung/ axit t do = 5/1 : 6/1 Thi gian : 15 20 pht NaNO3 : 4- 6 H3PO4 t do : 0,1 1 Thi gian : 8 10 pht

Phng php ny c nhc im l tc ho tan kim loi qu nhanh. C th dng phng php cromat ho mt giai on trong dung dch: H 2SO4: 5-10g/l, CrO3: 10-20g/l, thi gian 180s.

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