NXQ Nh n gia s mn Ha H c cho m i i t ng

Chemistry Teacher Education

1. n mn v bo v n mn kim loi
1.1. i cng v n mn kim loi 1.1.1. nh ngha v n mn kim loi C nhiu nh ngha v n mn kim loi, nhng c th hiu mt cch chung nht: n mn kim loi l s ph hu kim loi do tng tc ho hc ca kim loi vi mi trng xung quanh. Phng trnh m t hin tng n mn kim loi trong cc mi trng c dng nh sau: M - ne Mn+ Trong : M l kim loi, n l s electron trong nguyn t kim loi b mt i khi b xi ho, to th nh in kim loi Mn+. In kim loi sau c th tn ti dng t do trong dung dch hoc c th b kt ta di dng hir xit hay xit hay mui tu theo iu kin mi trng. 1.1.2. Phn loi n mn kim loi a. Phn loi theo c ch n mn Theo c ch ph hu kim loi, n mn kim loi c th phn th nh 2 loi: n mn ho hc v n mn in ho. n mn ho hc L qu trnh phn ng gia b mt kim loi vi mi trng xung quanh theo cc quy lut ca phn ng d th. Khi nguyn t kim loi tng tc trc tip vi phn t ca mi trng xm thc. Nhng v d in hnh nht v n mn ho hc l tng tc gia kim loi vi mi trng lng khng dn in hay vi cc kh kh. Phn ng nhit cao ca kim loi vi oxi hoc vi cc kh hot ng khc nh SO2, H2S, cc halogen n mn in ho L n mn kim loi l m pht sinh dng iin trong mi trng in ly. S n mn in ho hc tun theo nhng quy lut ca ng hc in ho. S n mn in ho hc thng gp trong cuc sng hng ng y, trong mi trng kh m, trong t, biin, dung dch in ly.

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NXQ Nh n gia s mn Ha H c cho m i i t ng

Chemistry Teacher Education

n mn in ho l qu trnh oxi ho kh xy ra khng cng mt v tr nn bao gi cng pht sinh dng din. Ni xy ra phane ng oxi ho kim loi (kim loi b mt electron tr th nh in dng), c gi l ant, ni xy ra s kh (xy ra phn ng tiu th electron) c gi l catt. Qa trnh ant- catt, cng nh qu trnh oxi ho - kh, l hai qu trnh ca mt phn ng in ho: Ant (oxy ho): M - ne Mn+ Catt (kh): D + e Dvi D (depolarizer) l cht kh, trong thc t thng gp l oxi hoc in H+. b. Phn loi n mn theo c im b mt b n mn Tu theo s ph hu b mt kim loi b n mn ngi ta phn bit hai dng n mn chnh l n mn tng th v n mn khu tr. n mn tng th Qa trnh n mn xy ra trn to n b b mt kim loi, n c th u hoc khng u. C 2 loi n mn tng th: + n mn u: L s n mn trn to n b din tch b mt kim loi tip xc vi mi trng xm thc,khng phn bit dc khu vc catt v ant. + n mn galvani: Trong dng n mn n y, trn b mt b n mn cha cc kim loi khc nhau mt s kim loi ng vai tr ant, mt s kim loi ng vai tr catt. Dng n mn n y thng xy ra trn b mt kim loi k thut hoc kim loi cha tinh khit. Ngo i ra n mn galvani cng c th xy ra khi b mt kim loi khng c ng nht. n mn khu tr S n mn xy ra tp trung tng phn ring bit trn b mt kim loi. Trn thc t ngi ta thng gp nhng dng n mn cc b sau: + n mn l: Xy ra khi b mt kim loi cha m ng th ng b ph hu. Ti ni b ph hu rt nh, n mn pht trin n su v o bn trong. + n mn hang + n mn nt: n mn dn n to th nh cc khe nt trong cu trc kim loi. + n mn gia cc tinh th: Vt nt do s n mn gy ra nm dc theo ranh gii gia cc tinh th.
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NXQ Nh n gia s mn Ha H c cho m i i t ng

Chemistry Teacher Education

+ n mn xuyn tinh th: Hnh th nh cc vt rn xuyn tinh th dn ti s ph hu to n b kim loi. c. Phn loi n mn theo mi trng Cn c v o c trng ca mi trng n mn, ngi ta phn ra cc kiu n mn ph bin sau: n mn kh quyn: n mn kim loi trong kh quyn hoc trong cc kh m t khc. n mn bin. n mn t: n mn kim loi t trong t. n mn trong cc dung dch in ly (cc dung dch axit, baz, mui). n mn dng d: gy bi s d in khin cc thit b kim loi trong mi trng xm thc b phn cc th nh ant v catt. n mn sinh hc: l n mn do cc vi sinh vt hay do nhng sn phm chuyn ho ca chng gy ra. + n mn cc b cn c dng n mn chit (extractive) l m ngho mt hay nhiu th nh phn hp kim (v l m gi u cc th nh phn cn li) trn b mt, trong tinh th hp kim, ch c mt th nh phn b n mn, mng tinh th b ngho i th nh phn b n mn mt cch ng u theo chiu t ngo i b mt v o trong vt liu. Do th nh phn v cu trc hp kim thay i, nn tnh cht ca hp kim vng b n mn cng thay i, c th dn n cc dng n mn khc. in hnh cho dng n mn n y xy ra trong dung dch nng chy, i vi hp kim Cu-Pt, Cu -Au. Vic chit tch La, to Ni trn b mt ht LaNi5 trong mi trng kim cng c th coi l dng n mn chit + Cc dng khc: n mn to th nh dng si (hay xy ra di lp ph du m bo qun), n mn bn di lp ph b mt (v d dy dn bng ng bc nha, n mn di lp m)

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NXQ Nh n gia s mn Ha H c cho m i i t ng oxy ha + kh

Chemistry Teacher Education kh xy ha

B mt trc khi b n mn

B mt sau khi b n mn

n mn u

n mn cc b

Hnh 1.1. S n mn u v n mn cc b Ngo i ra cn c th k n cc dng n mn c th khc, nh n mn chn lc, n mn ng sut (stress corrosion), n mn nt g y (cracking corrosion hay stress corrosion cracking SCC), n mn trong v tr... 1.1.3. Hin tng th ng B mt kim loi trng thi hot ho s tip xc trc tip vi mi trng. Nhng nu c m ng mng sn phm n mn, di dng oxit hay hiroxit hoc c hai, bm trn b mt s to th nh m ng (barie) ngn cn tip xc kim loi - mi trung, khi tc n mn s gim i ng k. Hin tng n y gi l hin tng th ng. C kim loi c th ng t nhin d d ng do tnh cht ho l bn kn ca m ng oxit, nh nhm (Al), nhng vi Fe cn c nhng iu kin nht nh mi c kh nng th ng (xem gin Pourbaix hnh 1.2). Mt s kim loi do bn cht nhit ng bn mi trng, nn khng b n mn trong t nhin, v d nh v ng (Au). 1.1.4. Cc yu t nh hng dn qu trnh n mn kim loi - Cc yu t bn trong:+ bn nhit ng ca kim loi + Cu to v tnh cht hp kim + c tnh ng sut + Trng thi b mt - Cc yu t bn ngo i:
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NXQ Nh n gia s mn Ha H c cho m i i t ng

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+ Bn cht dung dch in ly + Tc chuyn ng ca dung dch in ly + Th nh phn v nng ca dung dch in ly + Nhit , p sut mi trng + S tip xc gia cc kim loi vi nhau trong dung dch in ly hnh th nh pin n mn + Dng in tn (r in) 1.1.5. Nhit ng hc ca qu trnh n mn C th m t phn ng ho hc bng phng trnh tng qut sau : iBi = 0 (1.1)

trong h s hp thc i ca sn phm phn ng lun lun dng, ca cc cht tham gia phn ng lun lun m. K hiu Bi ch cht ho hc i tham gia phn ng. Enthapi t do ca phn ng G c nh ngha bng phng trnh G = ii G = Go + RTlnK (1.2)

S dng hng s cn bng K ta c th vit phng trnh (1.1) di dng sau : (1.3)

Trong tt c cc phn ng ho hc xy ra t pht, enthapi t do ca h phn ng lun lun gim. Nh vy phn ng ch c th xy ra khi G<0. Cc kim loi c oxit tn ti bn trong t nhin nh Fe, Zn, Al... u c G ca cc oxit v hiroxit nh hn khng, do v nhit ng hc u khng bn trong mi trng t nhin, u b n mn t thn, hay ni cch khc l qu trnh n mn cc kim loi n y xy ra t nhin khng th o ngc. 1.2. n mn in ho n mn in ho l qu trnh n mn xy ra trong mi trng in ly, c s trao i in t, nhng khng trc tip gia kim loi v cht oxi ho nh i vi n mn ho hc, m l gin tip qua in cc ant (cho in t) v in cc catt (nhn in t), do sinh ra dng in gia ant v catt. C th o c dng in pht sinh do n mn n y.

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NXQ Nh n gia s mn Ha H c cho m i i t ng

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S phn ng n mn in ho xy ra nh sau Ti ant M - ne Ti catt D + e M + nD DMn+ + nD(1.5) (1.6) Tng hp phn ng trong h khp kn (ant tip xc in vi catt) ta c Mn+ (1.4)

1.2.1. Nhit ng hc ca qu trnh n mn in ho gii thch cc hin tng hnh th nh mt sn phm n o ngi ta dng gin Puorbaix m ta mi lin h gia th v pH ca dung dch, cn bng in ho, ho hc xut hin trong qu trnh n mn. Cc ng n y chia gin th th nh 3 min: Min khng b n mn, min n mn v min th ng ho. Hnh 1.2 gii thiu gin Pourbaix E (V) pH i vi Fe trong mi trng nc. i vi mi cp in th E v pH ta xc nh c 1 to trn th, i chiu to nm trong vng n mn hay th ng s xc nh c trng thi ca st. V d vi in th -1V vi pH<14 Fe lun trng thi bn khng n mn (cn gi l tr n mn immunity). Vi E = 1V, pH< 7 Fe b n mn, nhng vi pH >7 Fe c th ng, tc n mn gim i ng k.
2.0

n mn

b
1.0

th ng

Ee

n mn
0.0

a
n mn

th ng

-1.0

vng bn vng
0.0 7.0

n mn
14.0

pH

Hnh 1.2 Gin cn bng in ho ca Fe (gin Pourbaix), xc nh

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NXQ Nh n gia s mn Ha H c cho m i i t ng

Chemistry Teacher Education

vng n mn, th ng v n nh nhit ng ca Fe trong mi trng nc 1.2.2. C ch ca phn ng in ho Mt phn ng in ho l mt phn ng phc tp xy ra qua nhiu giai on trung gian, mi giai on trung gian c coi l mt qu trnh s cp. C 4 giai on s cp chnh sau: 1. S ti khi: l s ti cht phn ng t lng dung dch ti b mt in cc (lp in kp) v s ti sn phm phn ng t b mt in cc. S ti khi c thc hin bng cc phng thc sau: - in chuyn: s chuyn in n y c nguyn nhn l , khi c in trng, xut hin chnh lch th; s bin thin th theo khong cch n b mt in cc. - Khuch tn: do s chnh lch nng , s bin thin nng n y cng theo khong cch ti b mt in cc. i lu: do s chnh lch nhit , chnh lch p sut hoc khuy c hc. oxit, kt ta, phn ng ho hc hay in ho th cp. 3. Qu trnh b mt: hp ph, kh hp ph, to mm tinh th v tng trng. 4. S chuyn in tch: s chuyn electron b mt in cc, xy ra vng ranh gii pha, trn b mt in cc, trong lp in kp. Tc ca phn ng in ho ph thuc tc ca giai on chm nht. 2. Mt s qu trnh ho l nh solvat ho hoc kh solvat to th nh hiroxit hay

1.2.3. Qu trnh n mn in ho Phn ng n mn in ho cng tun theo qui lut chung ca phn ng in cc. Xt trng hp nhng mt thanh kim loi khng ng nht v o dung dch in ly khng ng nht. Ly hai vng khng ng nht bt k nm st nhau trn b mt thanh kim loi, ta thy c nhng qu trnh sau: a. Qa trnh ant Ion kim loi b mt kim loi tip xc vi dung dch in ly b hidrat ha chuyn v o dung dch. B mt kim loi d in t. M ne Mn+

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NXQ Nh n gia s mn Ha H c cho m i i t ng

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Kim loi b mt in t ( b oxi ha), to th nh ion. Trong trng thi cn bng, th in cc tnh theo phng trnh Nernst: M = 0 +

RT ln ( a M n + ) nF

Nu t v o h mt in th ,, khc gi tr ti th cn bng th cn bng b ph v, phn ng in ha xy ra to mt cn bng mi: Nu ,, > : th xy ra qu trnh oxi ha, kim loi b n mn. Nu ,, < : th xy ra qu trnh kh, kim loi khng b n mn. b. Qa trnh catt Qu trnh catt l qu trn nhn in t, qu trnh kh. Ion, nguyn t, hay phn t nhn in t trn b mt kim loi: D + e DTrong D: cht kh cc. Thng thng trong n mn ta hay gp 2 cht kh cc chnh l oxi v H+. * n mn vi s kh phn cc oxi L qu trnh n mn kim loi m phn ng kh catt do O2 gy ra. Qa trnh n y rt ph bin trong t nhin, xy ra c trong mi trng kim, mui trung tnh, axit yu. Oxi khuch tn t khng kh v o dung dch n st in cc s xy ra ion ha oxi. Mi trng kim (trung tnh): O2 + 2H2O + 4e 4OHin th cn bng tnh theo phng trnh Nernst: 1O2 = 0
+

0.059 lg PO2 4 a OH

w = 0.43 + 0.059 lg PO2 - 0.059 . lg

( )

a (H)

Mi trng axit: O2 + 4H+ + 4e 2H2O

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NXQ Nh n gia s mn Ha H c cho m i i t ng

Chemistry Teacher Education

O2 = 0 + 0.059 lg PO2 * a H +

( )}
4

= 1.23 + 0.059 lg PO2 + 0.059lg a H +

( )

* n mn vi s kh phn cc hydro L qu trnh n mn kim loi c kh H2 thot ra do kh phn cc catt l ion H+. Qa trnh n y thng xy ra trong mi trng axit. Ion H+ khuch tn n st in cc, b kh th nh hidro qua hai giai on:
(1) 2H + 2e 2H ad (2) H2

n gin ho ta c phn ng : 2H+ + 2e H2 Ta c: in th in cc theo phng trnh Nernst: H2

0.059 ( a H+ ) = 0 + lg 2 PH2
= 0.059lg a H + -

( )

0.059 lg PH 2 2

( )

Qa trnh n mn kh phn cc hidro b chm ch yu do tc phn ng catt, do b mt catt d in t, in th in cc chuyn v pha m hn. c. Ant v catt l hai na khng th tch ri ca phn ng n mn C s chuyn dch in t t vng ant n vng catt; trong dung dch cation v anion cng chuyn dch theo chiu ngc li. Qa trnh xy ra lin tc, cc in t d vng ant chuyn di n vng catt; b li s in t b cht kh tiu th, nng lng t do ca h: G, phi tha m n iu kin G < 0. G = - nEF n: S ng lng gam ; F: Hng s Faraday ; E = ( VK )TN - ( VA )TN m vic ; E:Sc in ng

nguyn t n mn thun nghch

( VK )TN : in th in cc thun nghch trn in cc catt iu kin l

y ( VK )TN = Dcb

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NXQ Nh n gia s mn Ha H c cho m i i t ng

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( VA )TN : in th in cc thun nghch trn in cc ant iu kin l

y

m vic;

( VA )TN = Mcb
Hay Dcb - Mcb > 0 Dcb - Mcb > 0 T iu kin n y ta ho n to n c th tnh c qu trnh n mn in ho c

n > 0, F> 0 G < 0 E > 0

xy ra hay khng trong iu kin nht nh. Ta thy O2 lun dng hn so vi hidro, v th, n mn vi s kh phn cc oxi xy ra d d ng hn. Trong mi trng nc, kim, hu ht kim loi b n mn theo c ch oxi tham gia phn ng catt. Ch trong mi trng axit, in H+ mi tham gia phn ng catt. 2. Cc phng php bo v chng n mn kim loi T nh ngha n mn kim loi l s ph hu do tng tc ca kim loi vi mi trng, suy ra c 3 nguyn tc c bn bo v kim loi: Thay i th nh phn tnh cht ca kim loi Thay i th nh phn tnh cht ca mi trng Ngn cch kim loi tip xc vi mi trng xm thc

Cc phng php c th thng c s dng trong thc t s c gii thiu chi tit trong phn tip theo. 2.1. Phng php che ph Vic bo v kim loi bng cc lp che ph l mt trong nhng phng php ph bin nht. im mu cht ca phng php n y l nhm c lp b mt kim loi khi mi trng xm thc. Cc lp che ph bo v phi p ng mt s yu cu chung nh: lp bo v khng b n mn hay b n mn vi tc yu hn nhiu so vi tc n mn ca kim loi cn bo v; lp che ph phi d y v c bm dnh tt Tu theo yu cu thc t, ngi ta c th s dng lp che ph kim loi hoc lp che ph khng kim loi. Cc lp che ph kim loi

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NXQ Nh n gia s mn Ha H c cho m i i t ng

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C 2 loi ph kim loi l ph catt v ph ant. Nu lp che ph c th m hn th ca kim loi cn bo v (kim loi nn), lp che ph c gi l lp che ph ant; ngc li, khi th ca kim loi che ph dng hn th ca kim loi nn th ta c lp che ph catt. Cc lp che ph phi kim loi Cc lp che ph phi kim loi gm cc lp che ph bng cc cht v c v hu c. Cc lp che ph hu c thng l cc m ng polime. Sn v sn lc c dng rng r i nht trong thc t chng n mn kim loi do chng d che ph ln cc chi tit c nhiu loi hnh dng, kch thc, d d ng bt kn cc l, cc vt rn nt, v khng l m thay i tnh cht ca kim loi nn. 2.2. Phng php in ho hc Thc cht ca phng php n y l l m cho th ca kim loi cn bo v thay i theo hng a kim loi v o vng c bo v (bo v catt) hoc v o vng th ng (bo v ant). 2.2.1. Bo v catt Bo v catt l mt phng php c s dng thng xuyn chng n mn cc cu trc v cc thit b t trong mi trng xm thc (nc bin, t,). Phng php n y c p dng cho tt c cc kim loi nhng ph bin nht l cho thp trn hay thp m. Phng php bo v catt bng in cc hy sinh. Trong phng php n y, kim loi cn bo v c ghp ni vi mt in cc hy sinh l mt kim loi khc c th m hn rt nhiu. Bn cht ca phng php n y l phn cc kim loi cn bo v bng dng in tch m ngha l lin tc cung cp electron cho kim loi b n mn nh in cc hy sinh. Phng php bo v catt bng dng in ngo i. Bn cht ca phng php n y cng ging vi phng php bo v catt bng in cc hy sinh nhng y ngun cung cp electron cho kim loi cn bo v l ngun in mt chiu t bn ngo i. Kim loi cn bo v c ni vi in cc m ca ngun in ngo i. Tuy nhin phng php n y c nhc im l dng bo v i khi rt ln l m tiu tn in nng, do vy cn xem xt sao cho ph hp vi iu kin c th.
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NXQ Nh n gia s mn Ha H c cho m i i t ng

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2.2.2. Bo v ant Nguyn tc ca phng php bo v ant l phn cc kim loi cn bo v bng dng in tch dng, khi th ca kim loi s b dch chuyn v o vng th ca trng thi th ng. Kim loi cn c th b th ng ho bng cc phng php ho hc: X l bng dung dch c tnh oxy ho mnh. V d st s b th ng ho bng axit sunfuric c ngui hoc axit nitric c ngui. Hin tng th ng gn lin vi d hnh th nh mt m ng bo v vng chc trn b mt cch ly kim loi vi mi trng xm thc. 2.3. Phng php bin i mi trng xm thc hn ch s xm thc ca mi trng, ngi ta s dng cc cht c ch n mn. Cht c ch thng c kh nng l m gim tc n mn k c khi nng rt thp (10-3 10-6 mol/l). y l phng php rt ph bin c hiu qu kinh t cao. So vi cc phng php bo v khc, vic s dng cc cht c ch c nhiu u im ni bt. Khng cn xc nh li s k thut, cho php s dng cc kim loi c cu trc r tin thay cho cc kim loi c bit, nng cao kh nng bo v ca cc lp m hay sn lc m bo cc tnh cht c hc ca kim loi. Cc cht c ch thng c chia l m 2 loi: c ch catt v c ch ant. Cc cht c ch ant km h m tc ho tan ca kim loi do hnh th nh cc m ng bo v trn khu vc ant ca b mt kim loi b n mn hoc chuyn kim loi v o vng th ng bn. Nhng cht n y thng l cc hp cht hu c c cha nit, lu hunh hoc oxi,; Cc cromat, nitrit, nitrat s th ng ho cc kim loi. Nu lng cht c ch ant a v o khng , c th gy n mn r rt nguy him. Cc cht c ch catt l m gim tc n mn do l m tng s phn cc catt, v d nh cc hp cht ca photpho, asen l m gim dng trao i ca s thot hiro i vi qu trnh n mn vi s kh phn cc hiro. Cc cht c ch catt thng l m hnh th nh cc m ng pha, cc m ng hp ph c tc dng tch kim loi khi mi trng n mn.

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