1

CHNG 1 CC KHI NIM C BN

1. Khi nim v in ha
C th hnh dung cc chuyn nghnh ca Cngngh in ha trong s .

Pin s cp: pin

Nng lng

Leclanch Pin th cp: Ni-Cd;

Tinh luyn kim loi

Cng ngh

c in M in Chng n mn Sn xut cc cht v c, hu c X l mi trng

in ha

in ha

Phn tch in ha
Nghin cu cc qu

Sinh in ha

trnh chuyn cht qua mng t bo, kim sot cc qu tnh pht trin

2. Bn cht in ha ca n mn trong dung dch nc

Bi ging CN in ho-n mn

TS. L Minh c

Qu tnh n mn ca hu ht cc kim loi u lin quan n s vn chuyn electron. V vy cn thit phi nghin cu bn cht in ha ca n mn. Cc phn ng in ha 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.

Kim loi

Acid HCl M
2+

H+ H2 H+ H+

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
Bi ging CN in ho-n mn

(6) (7) (8) (9)

TS. L Minh c

Phn ng cathode quan trng i vi n mn l rt t. Phn ng n gin v hay gp nht l phn ng thot hydro trong mi trng acid. Ngoi ra c cc phn ng kh khc nh: Fe3+ + e Fe2+ Sn4+ + 2e Sn2+ trong dung dch acid v trung tnh: O2 + 2H2O + 4e 4OHv O2 + 4H+ + 4e 2H2O (12) (13) (10) (11)

l cc phn ng khng quan trng v t gp. Phn ng ca oxi ha tan thng gp

2.1. Phn cc
S dch chuyn in th in cc v pha m hn c gi l phn cc cathode (cathodic polarization).Tng t, nu elecltron trn b mt phn chia c gii phng nhanh s chuyn in th v pha dng hn v c gi l phn cc anode. Khi phn cc ln, kh nng ha tan anode s ln. V vy phn cc anode c c trng nh l ng lc ca qu trnh n mn. Trong dung dch, b mt s t th n mn n nh Ecorr.

2.2. Th ng
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.
Th Th ng

Ep Hat ng

Tc n mn

Bi ging CN in ho-n mn

TS. L Minh c

CHNG 2 NHIT NG HC N MN
Kim loi khi tip xc vi dung dch s hnh thnh mt b mt tip xc. Phn t nc phn cc khng i xng s b ht vo b mt, hnh thnh mt lp solvat, ngn cn cc ht mang in trong dung dch tin gn b mt kim loi. Mt mt phng gn nht ca cc ion dng so vi b mt mang in m gi l lp Helmholt ngoi. Hnh thnh nn mt lp in tch kp, ging nh mt t in v xut hin mt bc nhy th. in trng hnh thnh gia hai bn t in s khng ch cc qu trnh chuyn in tch trn b mt (cc phn ng in ha).

1. Nng lng t do v th in cc
Xt phn ng Zn trong acid HCl: Zn + HCl = ZnCl2 + H2 Khi xy ra phn ng, nng lng t do G s thay i . Khi sn phm c nng lng t do thp hn cht phn ng, G < 0, phn ng t xy ra. Bin thin nng lng t do G quan h vi th in cc ti trng thi cn bng G = - n. F. E Vi n l s electron trao i trong phn ng; F hng s Faraday. Hai na phn ng Zn = Zn2+ + 2e 2H+ + 2e = H2 ea ec

ea, ec c gi l th oxi ha, kh hay th in cc n ng vi hai na phn ng. Khi cht phn ng v sn phm xc nh trng thi tiu chun, c hot l 1 n v ta c eao ; eco.

1.1. Dy th in cc tiu chun

Do khng th o gi tr tuyt i ca th in cc (phn ng n), nn phi o s chnh lch th ca phn ng n vi mt in cc so snh. Thng s dng in cc hydro lm in cc so snh. Tuy gi tr tuyt i ca n l khc 0, nhng ngi ta quy c l 0.

Bi ging CN in ho-n mn

TS. L Minh c

in cc so snh hydro tiu chun (SHE) gm mt tm Pt nhng trong dung dch acid c hot bng 1. H2 thi vo di p sut l 1 atm. Thng in cc Pt c ph mt lp mui Pt tng din tch in cc v khng ch gii phng H2. Th in cc Zn khi ni vi SHE l 0,763 V.

1.2. Nng nh hng n th in cc

Xt phn ng tng qut: aA + mH+ + ne bB + dH2O Bin thin nng lng t do trng thi tiu chun Go v khng tiu chun G c tnh: Go = (bGoB + dGoH2O ) - ( aGoA + mGoH+) G = (bGB + dGH2O ) - ( aGA + mGH+) Bin thin G gia hai trng thi: G - Go = [b(GB + GoB ) + d(GH2O - GoH2O)] [a(GA - GoA ) + m( GH+ GoH+)] i vi cht A, hot ca A quan h vi G qua biu thc: a(GA - GoA ) = aRTln(A) = RTln(A)a Vi R l hng s kh; T l nhit tuyt i; (A) l hot ca A. Thay vo: G - Go = R.T. ln
(B) b .(H2O) d (A) a .(H + ) m

Thay G = -nFe ; Go = -nFeo; ta c e = eo (B) b .(H2O) d RT ln nF (A) a .(H + ) m

Hay c vit di dng khc: e = eo +

(A) a .(H + ) m 2,3RT log nF (B) b .(H 2 O) d

y l phng trnh Nerst . Khi thay pH = -log (H+) ta c e = eo +

(A) a 0,059 log n (B) b

m . 0,059 pH n

Bi ging CN in ho-n mn

TS. L Minh c

Trong trng hp ny, b qua nh hng ca hot cc cu t trong dung dch

1.3. in cc so snh SHE v cc loi khc

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 eH+/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. in cc so snh hydro tiu chun SHE (Standard Hydrogen Electrode) gi l in cc so snh loi 1. in cc so snh loi 2 hay s dng hn, th hin bng di y:
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 + 2Clecal. = 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 0,0 +0,222 Th V (SHE) +0,615 +0,318 +0,241

Bi ging CN in ho-n mn

TS. L Minh c

CHNG 3 NG HC N MN
ng hc nghin cu tc ca cc phn ng n mn. n mn trong dung dch trc tin quy nh bi cc phn ng in ha. Nghin cu ng hc l cn thit to ra cc hp kim chng n mn v pht trin cc phng php chng n mn.

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 6,2.108 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.

1.1. Mt dng trao i

Xt phn ng : 2H+ + 2e = H2 Ti th oxi ha kh hay th in cc n tiu chun eo H+/H2, phn ng t trng thi cn bng th tc phn ng thun bng tc phn ng nghch, lc ny: r thun = r nghch =
i o .a n.F

io l mt dng in trao i (Exchange Current Density) ti cn bng.

Bi ging CN in ho-n mn

TS. L Minh c

C nng lng t do v io khng th tnh ton bng l thuyt m ch xc nh bng thc nghim. 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 io b nh hng kh mnh ca b mt. Hay ni cch khc G khng b nh hng bi tnh cht b mt nhng khi io th rt nhy vi cc tnh cht ca b mt.

1.2. Phn cc
Phn cc l s dch chuyn in th in cc (E e) khi th cn bng e - 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).

1.3. 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 io

c = c log

ic 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.
Bi ging CN in ho-n mn TS. L Minh c

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 = -nFeH+/H2 Theo nh lut phn b Maxwell v nng lng ca cc ht phn ng: rthun v rnghch l hm ca nng lng hot ha. rthun = Kt. exp(G * thun RT RT

) )

rnghch = Kn. exp(-

G * nghch

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(Nng lng t do

i o .a nF
G * nghch RT

G * thun RT

) = Kn. exp(-

Trng thi hot

G*thu

G*n

H2 = 2H+ +2e nFc

Trng thi cn bng

G=-nFe Trng thi phn cc

2H+ +2e = H2

(1-)Fnc

Ta phn ng hay khong cch t in cc

Bi ging CN in ho-n mn

TS. L Minh c

10

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: ic = Kt . exp(i a = Kn. exp(G * thun nF c RT RT ) )

G * nghch +(1 )nF c

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

nF c (1 )nF c ) - io . exp( ) RT RT nF a (1 )nF a ) - io . exp( ) RT RT

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

l phn ca a mt i bi phn ng ion ha anode n gin li: itng.c = ic - ia = io. exp( khi c cao v
nF c ) RT

hot ha, c = c log(ic/io)

vi c =

2,3RT nF

Khi a cao: hot ha,a = a . log (ia/io) y l phng trnh Butler- Volmer

1.4. Phn cc nng

tc phn ng cao, phn ng kh cathode s lm gim nng cc ht mang in trong dung dch gn in cc. S thay i nng H+ c th biu din nh hnh di. CB l nng H+ trong ton dung dch v l chiu dy ca gradient nng trong dung dch. eH+/H2 tnh theo phng trnh Nerst l hm ca nng H+ hay hot (H+).
Bi ging CN in ho-n mn TS. L Minh c

11

eH+/H2 = e

H+/H2

(H + ) 2 2,3.R.T log( ) PH 2 nF

Nng

CB

CB = 0

Khong cch

Nng H+ trong dung dch b khng ch bi phn cc nng R rng e gim khi (H+) gim ti b mt. S gim ny gi l phn cc nng , n l mt hm ca mt dng in. n =
i 2,3RT log 1 c nF iL

Biu din quan h (n - logi) cho thy n thp khi t n mt dng gii hn iL. iL l tc phn ng cc i, t c v tc khuch tn ca H+ trong dung dch b gii hn. iL c th tnh: iL =
D.n.F.C B

D l khuch tn ca ht tham gia phn ng (H+ trong v d ny). Do vy iL tng khi nng CB dung dch cao; nhit cao; khuy trn dung dch.

1.5. Phn cc kt hp
Phn cc cathode tng tng,c l tng ca phn cc nng v hot ha tng,c = Khai trin ra ta c:
Bi ging CN in ho-n mn TS. L Minh c

hot ha,c

nng ,c

12

tng,c = c.log

ic + io

i 2,3.R.T log 1 c nF io

V phn cc nng thng khng tham gia trong phn cc nng ca phn ng ha tan kim loi. a = a.log
ia io

1.6. ng cong phn cc

1.6.1. Phn cc cathode Ga s h trong c hai na phn ng Zn = Zn2+ + 2e 2H+ + 2e = H2 Hy gi thit, c mt dng e tha (mt dng iapp.c) c p t ln in cc n mn Zn trong acid c E.m v i.m xc nh bng in th hn hp. Dng e tha gy cho in th chuyn v m hn t E.m n E. Th di chuyn mt khong c = E - E.m - c xc nh l qu th. Dng k hiu phn bit vi qu th t th n mn; l qu th t th in cc cn bng e.

ioH
i .m

ioH+/H2

nhnh anode

e io eM
ia

ia
ic

i .m

nhn h

ioM/M+

log

logiap

Bi ging CN in ho-n mn

TS. L Minh c

13

a)Mt dng p t, iapp.c, ln kim loi c th E.m v i.m ; gy ra qu th c ; b)ng cong phn cc c c t th a. Dng e tha lm gim tc phn ng anode t i.m n ia v tng tc phn ng kh t i.m n ic .Theo nguyn l bo ton in tch (tc trnh tch in trn b mt), s chnh lch gia tng tc kh cathode v gim tc oxi ha anode do qu th c phi bng nhau: iapp.c = ic - ia Hnh trn biu din dng iapp.c ng vi cc gi tr khc nhau ca c. Khi c thp th ic ch b hn ia mt t v iapp.c rt b. Khi tng c, ic tng trong lc ia gim. ia gim n lc rt b so vi ic , lc ny ng cong phn cc cathode trng vi ng gch cho na phn ng cathode ca phn ng 2H+ + 2e = H2 . V vy ng cong phn cc cathode (v vi logiapp.c) s cong ti vng qu th thp, nhng li thng vng qu th cao. Phn thng, ngi ta gi l tun theo Tafel. 1.6.2. Phn cc anode Electron b ly i khi kim loi v dng in s theo hng ngc li. S thiu ht electron khin in th chuyn v pha dng hn so vi E.m. Tc oxi ha tng trong khi tc kh ic gim do vy dng p vo: iapp.c = ia - ic Nhnh phn cc anode cng gii thch tng t nh nhnh phn cc anode.

Bi ging CN in ho-n mn

TS. L Minh c

14

CHNG 4 TH NG
1. Mng th ng
Th ng c nh ngha l s chng li n mn do hnh thnh mt lp mng mng trn b mt kim loi hay hp kim trong cc iu kin oxi ha vi phn cc ant ln.

2. Trng thi, biu din n mn th ng - hot ng

Th
3

ip Ep
1

i logi

Kim loi v hp kim c cc tnh cht th ng lun c cc biu hin ring bit khi phn cc ant. Dung dch axt tch kh th thp, tc n mn (mt dng ant) tng cao. Pha trn th th ng Epp, mng th ng tr nn bn, n mn thp trng thi th ng vng 2). Dng n mn trng thi th ng c th nh hn 106 ln so vi dng n mn trng thi hot ng ic. Ti th cao hn, mng th ng b ph v v tc ant tng qu vng qu th ng (vng 3). Vi thp khng r, hp kim Cr-Ni, qu th ng din ra vng gn th thot oxi, lc ny mng th ng giu Cr l khng bn.

Bi ging CN in ho-n mn

TS. L Minh c

15

2.1. nh hng ca nng cht oxi ha

Tng nng cht oxi ha s tng th oxi ha kh ca phn ng n theo phng trnh Nernst. L thuyt in th hn hp d on s nh hnh cho hp kim th ng- hat ng. Khi nng tng t 1 n 2, tc v th n mn tng t A-B nh thng thy cc hp kim v kim loi. Nng 3, hp kim c th tn ti trng thi th ng D hay hot ng C. Vng chuyn tip hot ng th
F Th E

ng, ti y dng gim khi tng th,

7

l vng to ra khi o thng k hiu gch gch. im X l trng thi th n nh v khng bao gi quan st c khi th ng c thit lp bi

6 4 3
C

D X

cht oxi ha ha tan trong thc t. Nng tng t 4 5, trng thi th ng n nh, tc n mn gim n gi tr hot ng thp gn im D. Tng 6 7 gy ra chuyn trng thi n qu th ng v tc n mn
log

A
1

tng t E F.

Quan h tc n mn theo nng th hin theo hnh. Khi nng cht oxi thi hot ng ban u. Trong vng BCD, c th hot ng hay th ng, mng th ng cha hnh thnh cho n D khi ch n lc ny mng th ng n nh v tc n mn gim ng k. T n mn duy tr gi tr thp trong vng th ng v tng trong vng qu th ng khi tng cao na nng . Khi qu trnh ngc li, nng long i do pha long th tc n mn gim theo ng c t qu th ng n th ng. Tuy nhin khi mng th ng hnh thnh th n vn duy tr nng thp.

Bi ging CN in ho-n mn

TS. L Minh c

16

V vy trong vng DCB, th ng bin xut hin. Khi b mt b co xc, s ph n nh mng th ng v n mn s tng trng thi hot ng C.

2.2. nh hng ca tc chuyn ng dung dch

th biu din n mn thp khng r trong dung dch axt pha long nh nc bin. Dung dch c tch kh. phn ng kh: 2H2O + 2e = H2 + 2OHv hp kim n mn trong trng thi hot ng. Tc thot H2 ca phn ng trn l thp i vi hu ht kim loi, v tc n mn rt thp trong dung dch trung tnh tch kh, ngay c trng thi hot ng. Khi c sc kh phn ng cathode s u tin: O2 + 2H2O + 4e = 4OH-

Th M=Mn++ne

Epass

O2+2H2O+4e=4OH-

Eam1 Eam2
2H2O+2e=H2+ 1 2 3 4 5 6

logi

Tng tc dung dch, s tng dng khuch tn gii hn t 1 6. Tc n mn v th n mn trong trng thi hot ng cng tng dn n 4, ni y th n mn

Bi ging CN in ho-n mn

TS. L Minh c

17

tng ng k n Epass v tc n mn gim t ic n ipass trong trng thi th ng nh hnh.

2.3. Cu trc v hp phn mng th ng

Cu trc m nhiu nh nghin cu a ra ca mng mng th ng trn st l lp di Fe3O4, lp ngoi l - Fe2O3. Lp trong Fe3O4 c cho l cu tc khuyt tt v v th dn in Mng th ng thng c c tnh ca bn dn loi n, mang cc in tch m tha. Mng th ng ca nhiu hp kim cha ng cc nguyn t hp kim, c bit l Cr hnh thnh mng oxt rt bn vi Fe. Cc hp kim v kim loi nguyn cht khc c nhng tnh khc nhau v hay thay i nh l mt hm ca th p t vo v thnh phn hp kim. Evans ng gp nhng cng trnh u tin trong vic a ra l thuyt mng oxt th ng, tch mng, cch ly mng oxt dy khi b mt st trong hp kim v Cr dung dch.. C hai c cng cu trc v thnh phn. Nhng mng cromat c hnh thnh do ph mng th ng trong sut qu trnh cch ly. Uhlig v ng nghip nhn mnh tm quan tng ca oxi hp ph ha hc trong vic hnh thnh mng th ng. Mng hp ph khng ch l mt ro ngn cn s ha tan ant m gii hn ng hc gim mt dng trao i io cho phn ng hon tan oxi hp ph ha hc thun li kh c mt cc electron phn lp d cha ghp i trong kim loi chuyn tip. Trong hp kim Fe-Cr, Cr l hp cht nhn cc electron phn lp d cha ghp i t Fe. Hp kim vi Cr nh hn 12%, khong trng electron d cha ghp i trong Cr b lp y t Fe d v hp kim ging nh st khng hp kim, m khng b th ng trong sung dch pha long tch kh. Ln hn 12% Cr, hp kim b th ng trong dung dch nh th, v cc electron phn lp d cha cp i lun sn c cho hp ph thun li, mng dy ln, cation kim loi c gi s i vo mng t kim loi nm di cng nh H+ t dung dch. H+ (H3O+) hay OH- ng vai tr trong vic hnh thnh mng th ng. Do Fe trong dung dch amniac, cc dung dch tng t khng phi nc, khng thy th ng hot ng. Mc d in th oxi ha kh c th o c cho oxi . Hin tng hot ng th ng khng c trong cc dung dch trng t khc.
Bi ging CN in ho-n mn TS. L Minh c

18

Phn ng ant tng : Fe + 2H2O = Fe(OH)2 + 2H+ + 2e Fe(OH)2 c th c hoc khng c trong cu trc mng. Lorenz v cng s gi thit Fe + H2O = (FeOH)h.ph + H+ + e (Fe(OH))h.ph = (FeO)h.ph + H+ + e (FeO)h.ph + H2O = (FeOO)h.ph + H+ + e Hp ph l giai on u trong qu trnh hnh thnh v pht trin mng, Tc n mn b c ch trong vng th th ng l v mng oxt hay gii hn ng hc l vn ang thao lun hin nay. Mng oxt c th gim io v mng hp ph c th hnh thnh ro cn.

Bi ging CN in ho-n mn

TS. L Minh c

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CHNG 5 PHNG PHP PHN CC O TC N MN

C hai phng php ang s dng hin nay o tc n mn bng phn cc in ha : ngoi suy Tafel v in tr phn cc. Phng php phn cc c nhiu thun li: - Cn thi gian ngn ( vi pht) xc nh tc n mn, cn phng php trng lng cn vi ngy. - Rt thun li trong nghin cu ng hc hay kim tra n mn trong nh my ang hot ng. - Phng php c nhy cao, khng cn cc yu t tng tc nh nhit . - Phng php khng ph v kt cu, lp li php o trn cng mt in cc.

1. Ngoi suy Tafel

Phng php ny c gii thiu m t l thuyt in th hn hp n mn trong dung dch nc. ngoi suy ng, yu cu phn ng n phi c khng ch bng qu trnh chuyn in tch. Trn ng cong phn cc t ra phi c mt on thng c chnh xc cc xc nh i.m bng ngoi suy Tafel.

Bi ging CN in ho-n mn

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20

iu ny thc s kh t c trong dng dch long lc ny phn cc nng v in tr Ohm nh hng ging nhau mt dng cao hn. Tuy nhin mt cch tng i trong gii hn ca ngoi suy Tafel i.m lun bng mt dng gii hn iL trong phn cc nng khi khuch tn khng ch qu trnh. Th phn cc ni chung ph thuc vo thi gian v cn xem xt cn thn c c g cong phn cc n nh phn nh phn cc n mn thc. Trong mt chng mc, ni chung phn cc cathode nhanh v thun nghch hn phn cc anode, ph thuc nhiu vo thi gian v tr.

2. Phng php in tr phn cc

Phng php in tr phn cc (TPC) c c t l thuyt in th hn hp. Xt ng cong phn cc vi qu trnh anode, cathode b khng ch bi qu trnh chuyn in tch. iapp.c = ic - ia ic l mt dng cathode; ia l mt dng anode. ; iapp.c l mt dng cathode p t ti ti cng gi tr in th E. Tng t: iapp.a = ia ic th thp gn to , phn tuyn tnh r rng. Phm vi tuyn tnh ph thuc vo gi tr hng s Tafel chn la. Khi phn cc t th n mn E.m vi ic, ia p vo: c= c. log(ic/i.m) a= a. log(ia/i.m) Khi phn cc t th n mn E.m, a,c l cc hng s Tafel anode cathode( phn cc hot ho) v i.m l tc n mn. c= a c xac nh nh l q th v n biu din s thay i th khi th n mn trng thi n nh E.m. Bin i ta c: iapp.c = i.m (10-c/c - 10-a/a ) V vy i app.c l s khc bit gia hai hm m m tin ti ) khi 0. Sp xp v ly vi phn ta c:

d = Rp = i app.c di app.c 0

B a.c = 2.3.ia.m (a + c) ia.m

Bi ging CN in ho-n mn

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21

V vy dc (d/diapp.c) 0 ti gc ng cong phn cc xc nh nh l in tr phn cc Rp l t l nghch vi tc d n mn B=

a.c 2.3.ia.m (a + c)

l hng s t l . Nhn thy hng s Tafel chn c gi tr ln s c phn tuyn tnh gc. Tuy nhin phn tuyn tnh xut hin qu th thp khi hng s Tafel thp a,c = 30mV. Chn a c gy ra s bt i xng qua gc to nh hnh 5.2 vi a=30mV ,c = 118mV. Ly logarith ta c: log Rp = log B - log i .m V vy v quan h log Rp logi.m l mt n thng c dc l -1 v im ct quy nh bi hng s t l B. Phn tuyn tnh trn mt di rng.

Ti liu tham kho [2]. D. Pletcher, F. C. Walsh, Industrial Electrochemistry, 1993. [3]. V. S. Bagotsky, Fundamentals of Electrochemistry, 2006. [4]. C. M. A.Brett, A.M. O.Brett, Electrochemistry-Principles, Methods and Applications, 1993. [5]. Philippe Marcus, Corrosion Mechanisms in Theory and Practice, 2002

Bi ging CN in ho-n mn

TS. L Minh c

IN PHN SN XUT NaOH Cl2

1. Phng php ho hc 1.1. Sn xut bng sa vi Na2CO3 + Ca(OH)2 = 2NaOH + CaCO3 1.2. Sn xut t qung pyrit: chia lm hai giai on Na2CO3 + Fe2O3 = Na2O.Fe2O3 + CO2 Na2O.Fe2O3 + H2O = 2NaOH + Fe2O3 em c c, ta c NaOH, Fe2O3 tun hon tr li trong qu trnh sn xut. u im ca phng php l khng c sn phm tha. NaOH c hn phng php sa vi. Nhc im l tn nhiu nguyn liu. 1.3. Phng php Venton MnO2 + 4HCl = MnCl2 + Cl2 + 2H2O Hon nguyn MnO2 MnCl2 + Ca(OH)2 = Mn(OH) + CaCl2 Thi khng kh v cho tha sa vi th Mn(OH)2 b oxi ho to kt ta MnO2. 2Mn(OH)2 + Ca(OH)2 + O2 = CaO.2MnO2 + 3H2O CaO.2MnO2 + 10HCl = CaCl2 + 2MnCl2 + 5H2O + 2Cl2 2. Phng php in ho *Dch in phn: Mui n NaCl (cha 39,4% Na, 60,6%Cl). Mui uc ho tan n gn bo ho v a v thng in phn ( 45 -55oC). *Nc mui cn x l trc khi a vo thng in phn, tch hm lng Mg2+, Ca2+, SO42-, . . . SO42-: hp ph ln anode, cn tr phng in ca Cl, to iu kin O phng in, anode b n mn. Cho php: Ca2+ <0,005g/l, Mg2+<0,001g/l
Bi ging CN in ho-n mn TS. L Minh c

2.1. Phng php tinh ch nc mui

2.1.1. Phng php xa-kim

Ca2+ + Na2CO3 = CaCO3 + 2Na+ Mg2+ + NaOH = Mg(OH)2 + 2Na+

2.1.2. Phung php sa vi-xa

MgCl2 + Ca(OH)2 = Mg(OH)2 + CaCl2 MgSO4 + Ca(OH)2 = Mg(OH)2 + CaSO4 Ca(HCO3)2 + Ca(OH)2 =2CaCO3 + 2H2O CaCl2 + Na2CO3 = CaCO3 + NaCl CaSO4 + Na2CO3 = CaCO3 + Na2SO4
2.1.3. Phng php sa vi-sunfat

Gm 2 giai on: +Tch Mg, Ca nh sa vi +Gia cng sunfat lng trong dung dch bng xa Na2SO4 + Ca(OH)2 = NaOH + CaSO4 CaCl2 + 2NaOH = Mg(OH)2 + 2NaCl MgSO4 + 2NaOH = Mg(OH)2 + Na2SO4 CaSO4 + 2NaOH = CaCO3 + Na2CO3 +2H2O CaCl2 + Na2SO4 = CaSO4 + 2NaCl +Trao i ion 2R-Na + Ca2+ = R2-Ca2+ + CaCl2 R l gc nha. Sau khi trao i, nha c mang i ti sinh 2.2. Cc phn ng in cc S phn ly: NaCl = Na+ + ClH2O Cathode : in phn nc
Bi ging CN in ho-n mn TS. L Minh c

H+ + OH-

2H2O + 2e = 2H + 2OH2H = H2 OH- + Na+ = NaOH Na phng in trn in cc c khng? Trong mi trng pH=7, H+ phng in -0,41V Phng trnh Nernst :
E = Eo + RT 0 ln C Na + , E =-2,7V nF

Thay vo ta c: CNa+ = 3,8.1038 mol/l Anode: Cl phng in to kh Cl2, OH- cng c th tham gia 2Cl- -2e = Cl2 4OH- - 4e = O2 + 2H2O hoc 2H2O -4e = O2 + 4H+ Chn loi in cc sao cho: qu th thot clo nh hn, clo s u tin tham gia phn ng trc. Loi in cc ph hp: graphit, Ti m Pt, Ti ph RuO2,TiO2. Cc phn ng ph -ion OH- tham gia phn ng anode 4OH- - 4e = O2 + 2H2O Oxy thot ra anode, ln vo kh Cl2. Oxy phn ng vi grapht, tiu hao anode -Ho tan Cl2 vo dung dch Cl2 + H2O = HClO + HCl Cl2 + OH- = HClO + Cl-ClO- phng in trn anode 6ClO- + 6OH- = 2ClO3- + 4Cl- + 3/2 O2 + 3H2O + 6e 3. Cu to thng in phn NaOH, Cl2 mng ngn

Bi ging CN in ho-n mn

TS. L Minh c

Nguyn l hot ng ca mng ngn aming Aming ph trc tip ln in cc cathode Fe (dng li). in cc anode t gn mng ngn, nc mui 30% chuyn vo khoang anode, Cl2 sinh ra trn anode. Nc mui khuch tn qua mng ngn xp, H2 v NaOH hnh thnh pha bn kia ca mng ngn. Anode l Ti c ph lp xc tc. Cathode Fe c ph lp xc tc (Ni din tch ln) lm gim qu th hydro. Dng mng ngn aming gp phi mt s vn : +Khi c s chnh lch nng , tt c cc loi ion u c th khuch tn qua mng ngn. Na+ di chuyn t khoang anode sang khoang cathode bng khuch tn, i lu v in di. Hu ht lng Clo tng ng i cng vi Na+ vo khoang cathode v vy NaOH ln nhiu Cl. Ngoi ra, nng NaOH ch t di 12%, khuch tn ca OH- t khoang cathode n khoang anode tr nn ng k. iu ny dn n mt mt Cl do in phn thnh hypocloride v hnh thnh oxy anode, lm bn sn phm Cl. NaOH c nng thp nn cn thit b c c nng ln nng 50%. +in tr ri IR trn mng ngn ln. in th thun nghch ca thng in phn l -2,2V, ca thng in phn c mng ngn l -3,2 n -3,8V, in

Bi ging CN in ho-n mn

TS. L Minh c

th ny ri ch yu trn mng ngn. Theo thi gian, IR mng tng do cc cht kt ta hyroxit ca Mg, Ca trong cc l xp ca mng. Nc mui cn phi lc sch trc khi vo thng. +Mng cn thay sau vi thng. Trong qu trnh thay mng vn phi m bo hot ng ca nh my. Do in tr ca thng in phn mng ngn ln, tiu hao nng lng khi hot ng mt dng cao l khng kinh t. Thng lm vic 0,15 0,2 A/cm2. Khi thit k phi m bo din tch in cc ln nht trn mt n v th tch.

Sp xp in cc anode

Bi ging CN in ho-n mn

TS. L Minh c

Thng cathode

Bi ging CN in ho-n mn

TS. L Minh c

Thng in phn mng ngn, kiu MDC 55 ca Oxy Tech Systems, Inc Thng MDC 55 c kch thc 3 x 16 x 2 m, nng khong 7 tn. in cc l loi n cc, dng in 120 kA, in th 3,4 V, nng sut 3,5 tn Cl2 mi ngy. S cng ngh in phn sn xut NaOH, Cl2 c th hin hnh
Dy chuyn cng ngh

Chun b dung dch

un nng

Kt ta Mg, Ca

Lc
HCl

Phn ly

Ra Lm sch
H2
H2SO4

Thng in phn
Cl2

Axt ho
NaOH NaCl

un nng

Sy

Lm lnh

Bc hi

Ly tm NaCl NaCl

Ho lng

Na2SO4

Tng hp HCl

NaCl

4. Thng in phn cathode thu ngn 4.1. Thng in phn, dy chuyn cng ngh

Bi ging CN in ho-n mn

TS. L Minh c

S cng ngh in phn NaOH, Cl2 vi cathode thu ngn 4.2. Cc phn ng trn in cc 2Cl- -2e- = Cl2 Na+ + Hg + e- = NaHg Phn ly hn hng 2NaHg + 2H2O = H2 + 2Na+ +2OH- + 2Hg Kch thc thng 15 x 2 x 0,3m, bng st, y nghing Hg chy t u ny n u kia. Anode lm bng vt liu bn, ph Ti. Kch thc 30 x 30 cm t song song vi b mt Hg (khong cch 1cm). Thng c khong 250 anode.

Bi ging CN in ho-n mn

TS. L Minh c

Nng mui vo 25%, 60oC. Chy qua cell. Kh Cl2 thot ra nh, hn hng Hg nm y. Hn hng c tch hon ton NaCl v i vo thit b tch (denuder). L mt thit b hnh tr, c nhi cht bng graphit c gn cc kim loi chuyn tip Fe hay Ni lm xc tc phn hu hn hng. NaHg e- = Na+ + Hg ; 2H2O + 2e- = H2 + 2OH-

5. Cng ngh mng trao i 5.1. Cng ngh

Bi ging CN in ho-n mn

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Ti liu tham kho [1]. D. Pletcher, F. C. Walsh, Industrial Electrochemistry, 1993. [2]. V. S. Bagotsky, Fundamentals of Electrochemistry, 2006. [3]. C. M. A.Brett, A.M. O.Brett, Electrochemistry-Principles, Methods and Applications, 1993.

Bi ging CN in ho-n mn

TS. L Minh c

BIN TNH B MT KIM LOI

1. 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. Mng Al2O3 c th hnh thnh trn b mt nhm bng phng php in ha hay ha hc. Mng c th dy n hng trm micron. 1.1. 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 : 2 2,5 g/l : 5 30 pht Na2CrO4 : 15 g/l Thi gian 1.2. Phng php in ha
1.2.1. C cu mng oxit

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
Bi ging CN in ho-n mn TS. L Minh c

4OH- - 4e = O2 + 2H2O Qu trnh gii phng oxi c th qua cc bc: 2OHO2O2O = H2O + O - = O- + e = O + e = O2 = Al2O3

Cc sn phm trung gian O2-, O tc dng vi nhm anode (vt cn oxi ha) 2Al3+ + 3O22Al + 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 Ha tan mng ny s to ra cc l xp. cathode, qu trnh kh : 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
1.2.2. Dung dch v ch in phn :

H2SO4 Nhit

: :

180 200g/l phng 1,5 2 A/dm2

Mt dng anode Da :

Thi gian oxi ha : 40 50 pht

Bi ging CN in ho-n mn TS. L Minh c

1.3. 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 kt ta mu vng da cam -Thnh phn dung dch nhum mu
Thnh phn (g/l) 10 50 10 50 15 25 50 100 10 50 Cu2 Fe(CN)6 CoO PbCr2O7 PbSO4

Ag2CrO4

+ 2KNO3

Mu Xanh Nu en Vng Vng nht

Dung dch 1 FeCl2 CuSO4 Pb(CH3COO)2 Pb(CH3COO)2 Pb(CH3COO)2

Thnh phn g/l 10 100 10 100 40 100 100 200 10 50

Dung dch 2 K4Fe(CN)6 K4Fe(CN)6 KMnO4 K2Cr2O7 Na2SO4

Hp cht mu

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.

Bi ging CN in ho-n mn

TS. L Minh c

2. 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. 2.1. Pht pht ho nng Chia lm hai loi: PPH thng v PP nhanh -PPH thng 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+ + PO43Bi ging CN in ho-n mn TS. L Minh c

Kt qu l lp dung dch gn b mt mu thp giu ion Fe2+ 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 MeHPO4 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 - T s axt chung v axt t do - Nhit Thnh phn v ch PPH [nFe(H2PO4)2.[mMn(H2PO4)2] Nhit -PPH nhanh 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.
Bi ging CN in ho-n mn TS. L Minh c

: 30 - 35 g/l

: 97 99oC

Thi gian : 40 - 80 pht

Thnh phn (g/l): [Fe(H2PO4)2][Mn(H2PO4)2] NaNO3 : 4- 6 Zn(NO3)2.6H2O : 60 H3PO4 t do : 0,1 1 Nhit : 92 - 96 oC Thi gian : 8 10 pht Dung dch khc Zn(H2PO4)3.2H2O : 35 37 Zn(NO3)2.6H2O : 52- 53 H3PO4 t do : 15 - 16 T l axit chung/ axit t do = 5/1 : 6/1 Nhit : 85 - 95oC Thi gian : 15 20 pht 2.2. 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 : Majep : 35 45 g/l Zn(NO3)2 : 70 90 NaF Thi gian : 20 40 pht Dung dch 2 H3PO4 t do : 80 85 ZnO : 15 17
Bi ging CN in ho-n mn TS. L Minh c

: 30

NaNO2 : 1 2 pH: 2,7 - 3,1 Thi gian : 15 20 pht 3. 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 Cr3+ 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. 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: H2SO4: 510g/l, CrO3: 10-20g/l, thi gian 180s.

Bi ging CN in ho-n mn

TS. L Minh c

PHNG PHP NG T IN HO X L NC THI

1. Khi nim chung
Phng php ng keo t, to bng l mt phng php c s dng rng ri trong vic x l nc thi ni chung, nc thi cng ngh dt nhum ni ring. C s ca phng php l s dng mui kim loi c kh nng hnh thnh cc bng keo t. Cc bng keo t ny s hp ph cc cht bn trong nc thi v c tch ra bng cc phng php n gin. Bng phng php ny cc tp cht tn ti trong nc thi di dng keo, dng t tan c tch ra. Cc ht keo mun tch ra mt cch c hiu qu, trc ht cn trung ho in tch ca chng v sau lin kt chng li vi nhau, hnh thnh khi keo t ln hn. Qu trnh trung ho in tch gi l qu trnh ng t, cc bng keo tp hp thnh khi bng ln hn gi l qu trnh to bng. Cc cht ng t thng s dng l mui ca nhm, st hoc s dng hn hp. Hay s dng nht l mui nhm Al2(SO4)3 - mt mui tan tt trong nc, gi thp, hot ng trong gii hn pH rng t 6-8. Cc mui st hay c s dng: Fe(SO4)3.2H2O, Fe2(SO4)3.3H2O, FeSO4.7H2O v FeCl2. ng t in vi anode nhm ho tan l mt phng php to ra cc cht keo t nh Al(OH)3, Fe(OH)2, Fe(OH)3 gy keo t, hnh thnh cc bng keo c kh nng keo t nhiu cht hu c, cht mu trong dung dch. Bn cnh , kh H2, O2 thot ra hai in cc cathode v anode lm tuyn ni, khuy trn dung dch lm tng thm hiu qu x l. Lp bn nho Al(OH)3 hp ph cc cht mu, cht hu c, cc tp cht khc trong dung dch di tc dng ca tuyn ni s ni ln trn mt dung dch .

2. Cc c tnh chung ca ht keo v c 2.1. Cu trc ca ht keo v c trong dung dch: ht keo gm ba phn :
-Nhn ht keo: l tp hp nhiu phn t rn lin kt vi nhau, c bao bc bi mt lp v ion. S hp ph mt loi ion no trong dung dch to nn lp v ion ny. -Lp in tch kp: hnh thnh bi cc ion tri du vi lp v ion. -Lp ion khuch tn hnh thnh phn ngoi ca lp in tch kp.
Bi ging CN in ho-n mn TS. L Minh c

Cu trc ht keo th hin trn hnh 4.1 .

Ht mang in tch m

Th in ng tng Th nng xung quanh ht keo Th in ng zta Mng bao quanh ht keo

Lp khuch tn cc ion tri du Lp in tch kp

Hnh 1: M t cu trc ht keo. Khi nim v lp in tch kp

2.2. Tnh cht ca cht keo:

-Cc ht keo tn ti l lng trong dung dch , chu tc ng bi hai lc i nhau: lc ht phn t Van der Waals c khuynh hng kt hp cc ht keo li khi chng mt khong cch rt gn nhau. Lc y tnh in ngn cn s kt hp cc ht keo tch in cng du. -Tn ti mt in th in ng zta -l in th tnh t mt trt ca ht v trong lng dung dch.

2.3. C ch ph bn ht keo
2.3.1. Nn p lp khuch tn: Khi trong dung dch c cc cht in ly l, lp khuch tn ca ht keo s b nn p li, to iu kin cho cc ht huyn ph tip cn nhau, tnh bn ca h keo s km i. B dy lp khuch tn gim khi ha tr v nng ca ion i cao. S keo t theo c ch ny ch din ra ch yu vi cc h keo c th nng cao, dy lp khuch tn khng ln v nng ion ca dung dch nh. S keo t ch din ra khi nng cht in ly t mt gi tr ti thiu no gi l ngng keo t. Ngng keo t quan h vi ha tr v nng ion theo cng thc: C = K
3 ( K p .T ) 5
A2C 6 Z 6 TS. L Minh c

Bi ging CN in ho-n mn

Vi K l hng s, A l hng s tng tc ht tnh in, l hng s in mi, Z ha tr ca ion i. 2.3.2. Hp ph v trung ha in tch S ph bn ca h keo do hp ph v trung ha in tch khi s dng Fe3+ v Al3+ din ra nh sau: qu trnh thy phn ca cc ion kim loi to thnh phc hydroxo Al(OH)2+, Al(OH)2+, Fe(OH)2+ . . .sau hnh thnh cc polyme hydroxo v cui cng l kt ta hydroxt kim loi. Cc ion dng trn hp ph gy trung ha in tch m trn b mt ht keo, gim lc y ca cc ht, to iu kin thun li cho cc ht keo tin gn nhau hn to cc ht keo ln. C ch ny ch din ra khi h huyn ph mang in tch m ng vi gi tr pH ln hn pH ng in ca h huyn ph. Cc ht keo nhm hay st c th lm o du in tch lm h huyn ph bn tr li. Nguyn nhn ny l do s dng tc nhn keo t qu liu lng. Lc tng tc l t hp cc lc tnh in v lc ha hc lm cc ht huyn ph o du tch in v gy ra s ti bn h. 2.3.3. C ch dnh bm vo kt ta Khi cc mui st, nhm hay cc oxit, hydroxit kim loi dng lm cht keo t c nng cao chng s kt ta nhanh di dng cc bng keo hydroxit. Cc ht keo c th dnh vo khi kt ta cc hydroxit ty thuc qu bo ha ca dung dch. kt ta nhanh, th t s:
[ Me n + ][OH ]n 100 Ks

[Men+], [OH-] l nng mol ca ion kim loi, hydroxyl trong dung dch; Ks l tch s tan ca ion Me(OH)n. Khi cc ht kt ta tch in dng, kt ta s tng vi s c mt ca cc anion trong dung dch. Cc ht keo c xem nh l cc tm to thnh kt ta. 2.3.4. C ch kt ta qut, hp ph to cu ni. Ngoi hai c ch trn, qu trnh keo t cn xy ra theo c ch kt ta qut, hp ph to cu ni gia cc ht keo. Theo c ch kt ta qut, qu trnh thy phn v to polyme xy ra khi nng trng thi siu bo ha. Khi lng chng li cun
Bi ging CN in ho-n mn TS. L Minh c

cc ht keo lng theo. Khi cc polyme hnh thnh trong h hay c b sung t ngoi vo, chng c hp ph ln b mt ht keo v to nn cu ni gia chng, to thun li hnh thnh tp hp ln hn. 2.3.5. Cc phn ng xy ra trn in cc Khi c dng in mt chiu i qua dung dch, trn anode, cathode xy ra cc phn ng nh sau: anode: .Ho tan nhm : Al - 3e Al3+ .Thot oxy: pH<7 : 2H2O - 4e O2 + 4H+ pH>7: 4OH- - 4e O2 + 2H2O cathode pH<7 : 2H+ + 2e H2 pH>7 : H2O + 2e H2 + 2OHIon Al3+ va mi hnh thnh trn lp dung dch st anode nhm, chng tham gia cc phn ng thy phn: .pH<4 : Al3+ b hydrat ho chuyn thnh Al3+.6H2O .pH= 5,7 - 8 cc phn ng thu phn nh sau: Al3+ + H2O Al(OH)2+ + H+ Al3+ + 2H2O Al(OH)2+ + 2H+ 2Al3+ + 2H2O Al2(OH)24+ + 2H+ Al3+ +3H2O Al(OH)3 + 3H+ 3Al3+ +4H2O Al3(OH)45+ + 4H+ Al3+ + 4H2O Al(OH)4- + 4H+ Qa trnh thu phn c tip tc: Al(OH)2+ + H2O Al(OH)2+ + H+ Al(OH)2+ + H2O Al(OH)3 + H+ Al(OH)3 + H2O Al(OH)4- + H+ logK7= -4,3 logK8=-5,7 logK9=-8,0 logK1 = -5,0 logK2= -10,1 logK3=-7,7 logK4 =-10,4 logK5=-14 logK6=-22,7

Cc ht mang in ny, trn ng chuyn v cc i, chng tip tc b thu phn, to thnh cc sn phm phc a nhn v sn phm cui cng l Al(OH)3.
Bi ging CN in ho-n mn TS. L Minh c

Dng hydroxo Al tn ti mt cn bng vi Al(OH)3 v c ho tan ph thuc pH. pH <5,5 cc phc nhm hydroxo tch in dng Al(OH)2+, Al(OH)2+ (chim 95%). pH 6-9 Al(OH)3 to ra nhiu nht. Khi pH>10 Al(OH)4- c hm lng ln nht. 2.3.6. S to thnh keo nhm bng ho tan anode i vi dung dch c pH= 5-7, khi in phn do s thot kh O2 trn anode, H2 trn cathode, nhm ion b thy phn nn pH dung dch thp, thnh phn ch yu l Al(OH)2+ v Al(OH)2+ ngoi ra cn c Al3+ v Al(OH)3. Nu dung dch c tnh acid, hm lng phc hydroxo tch in dng kh cao, chng nm phn tn, chm lin kt li to ht keo ln hn. Khi tng pH>6, ion Al3+ va hnh thnh s b thu phn hon ton, phc hydroxo Al(OH)2+, Al(OH)2+ tip tc thu phn, sn phm thu phn l Al(OH)3. n pH=7-8 Al(OH)3 t nng cc i. Nh vy khi tng pH, hm lng cc ht keo dng gim dn, cc sn phm thu phn d lin kt vi nhau li hn to thnh cc ht keo ln hn. Th t cc phn ng thu phn nh sau: Al3+.6H2O + H2O Al(OH)2+.5H2O + H3O+ Al(OH)2+.5H2O + H2O Al(OH)2+.4H2O + H3O+ Al3+.6H2O + 2H2O Al(OH)2+.4H2O + 2H3O+ Al(OH)2+.4H2O + H2O Al(OH)3.3H2O + H2O+ Trong qu trnh in phn, pH ca lp dung dch st anode gim dn do to ra keo nhm v thot O2 nn cc hydroxo tch in dng c phn tn rt cao. Trong in trng, H+ chuyn v cathode s trung ho cc ion OH-chuyn t cathode sang anode, gip cho qu trnh thu phn hnh thnh cc hydroxo d dng. Trong khong pH =5,7-7,0 cc thnh phn chnh l Al(OH)2+, Al(OH)2+ . . . v Al(OH)3. Tng pH v thi gian in phn, cc phn t lin kt to cc ht a nhn: kAl(OH)2+ + mAl(OH)2+ + nAl(OH)3 Alp(OH)qr+ p=k+m+n; q=k+3n+2m; r=2k+m

Bi ging CN in ho-n mn

TS. L Minh c

V th c th xem ht keo Alp(OH)qr+ l ht keo a nhn c trng trong khong pH= 5,7-7,0. in tch ht ny ty thuc lng Al(OH)2+; Al(OH)2+ c ngha l ph thuc pH dung dch v lng Al3+. Khi gi tr pH nm trong khong 7-8, cc hydroxo Al(OH)2+, Al(OH)2+ v Al(OH)3 hnh thnh lp dung dch st anode Al ho tan theo cc phn ng nh sau: Al3+.6H2O + H2O Al(OH)2+.5H2O + H3O+ Al(OH)2+.5H2O + H2O Al(OH)2+.4H2O + H3O+ Al(OH)2+.4H2O + H2O Al(OH)3.3H2O + H3O+ H3O+ + OH- 2H2O Ion OH- chuyn sang anode, kt hp vi ion H+ to ra nc. Al3+ tham gia phn ng thy phn thun li nn nng Al(OH)2+, Al(OH)2+ rt nh, lng Al(OH)3 t 90-95%, bt u c s hnh thnh Al(OH)4-. Tt c cc ion dng, m kt hp vi Al(OH)3 hnh thnh ht a nhn in tch dng nh: kAl(OH)2+ + mAl(OH)3 + nAl(OH)4- [Al(OH)3]mAln+k(OH)4n+2kk-n Ht keo c th zeta xp x bng khng nn cc ht c phn tn gim, chng d tng tc vi nhau to thnh cc khi huyn ph v nh hnh kch thc ln. pH t 8,0 -8,5 lc ny lng OH- cao, tham gia phn ng vi H+ hnh thnh nc, to iu kin thun li thu phn cc phn t hydroxo thnh Al(OH)3. Cc ht Al(OH)3 tip tc thu phn to thnh cc ht mang in m: Al(OH)3.3H2O + H2O Al(OH)4-.2H2O + H3O+ Trong khong pH ny, ht keo c th zeta nh nht. Keo nhm tch in m do hp ph cc anion Al(OH)4-. Ht keo a nhn c cng thc mAl(OOH).nAl(OH)42.3.7. S tn ti ca cht keo mu trong nc thi Trng thi phn tn ca thuc nhum lin quan n cu trc, bn cht ha hc ca chng v chu nh hng ca bn cht dung mi, pH mi trng v c mt ca cc cht ph gia.

Bi ging CN in ho-n mn

TS. L Minh c

2.3.7.1. nh hng ca dung mi: Dung mi c nh hng ln n kh nng ha tan v phn tn ca thuc nhum. Dung mi khng cc ha tan cc cht khng cc, dung mi c cc c kh nng ha tan cc cht c cc. Nc l dung mi phn cc ph bin nht do cu trc c cha nhm -OH. Cc phn t cht mu c cha cc nhm phn cc nh: -SO3Na, -COOH, -OSO3Na, -N+H2-HCl, -N+R3Cl . . .th d tan trong nc. Cc cht mu khng cha cc nhm tan hay cc nhm trn b chuyn v dng mui canxi, bari th khng tan trong nc. tng ha tan ca thuc nhum, ngi ta nghin chng siu mn v b sung thm cc cht ph gia vo hn hp. 2.3.7.2. S bin i tnh cht thuc nhum Do c mt cc cht ph gia, pH mi trng thay i, nhit . . .m cc cht mu c th tham gia cc phn ng ha hc lm thay i tnh cht ban u ca mnh: nh tham gia phn ng ha hc lm thay i mu sc ca phn ng gia thuc nhum hot tnh vi vt liu; thay i tnh cht ca thuc nhum hon nguyn. 2.3.7.3. Tnh cht keo ca cht mu hu c a s cc cht mu tn ti trong nc dng keo hoc bn keo. Ty thuc vo bn cht, cu to, kch thc v khi lng phn t ca cht mu hu c m n dng ha tan hay phn tn trong dung dch. Khi cc phn t c phn khng phn cc ln v phn phn cc nh th phn t thuc nhum ring l c th to thnh mixen keo. S lin kt xy ra i vi nhng thuc nhum m phn t cha nhiu nhm k nc, v d nh thuc nhum polymethine. Mt vi loi ca thuc nhum ny khng lin kt trong ru nhng lin kt trong nc to thnh cc mixen lm cho nht tng, di ph hp th mu b thay i. Cc phn t thuc nhum c nhiu vng ccbua hydro k nc v mt s nhm phn cc a nc nh -SO3Na, -OH, -COONa . . . c th tan trong nc, ru, axeton. . .Ty khi lng v cu to phn t m chng c th tn ti dng keo a nc hay ha tan to thnh dung dch thc. Cc phn t kh nh nh metyl

Bi ging CN in ho-n mn

TS. L Minh c

da cam m bao gm mt s t vng thm v nhiu nhm phn cc mnh nh -OH, SO3Na th khng to thnh mixen. Cc iu kin khc nh nng cht mu, cht in ly, nhit dung dch c th nh hng n bn ca cht mu: nng cht mu tng lm gim bn keo. S c mt ca cc cht in ly c th lm thay i bn ca h keo mu. Nhit tng lm tng ha tan ca cht mu nn bn keo tng ln [3]. Mixen ca cc loi thuc nhum - naphton orange kh nh khng to thnh mixen keo bn mc d xy ra s ng t khi c mt NaCl. S lin kt to thnh mixen bn vi cc kch thc v hnh dng khc nhau c quan st vi benzopurpurin. S to thnh mixen ph thuc vo nng thuc nhum, mui NaCl: khi nng NaCl ln th nhng mixen khng l ca benzopurpurin xut hin, nhit cao hn 60oC th khng thy to thnh mixen. S to thnh mixen c nhn thy vi thuc nhum mu vng. Tm li, s lin kt to thnh mixen ca cc thuc nhum khc nhau dng nh c khng ch bi cc qu trnh tng t nh s kt hp ca cc phn t cht ty ra, cc phn t bao gm cc nhm c cc - khng cc . . . 2.3.7.4. Tng tc vi dung mi Cc keo phn cc th bn trong mi trng phn cc, ngc li cc keo khng phn cc th bn vng trong mi trng khng phn cc v km bn trong mi trng phn cc. tng bn phn tn ca cc cht keo trong mi trng khng c cng bn cht, ngi ta s dng cc cht keo a dung mi, cc cht keo ny c mt phn hp ph bm dnh vo phn t ca cht cn bo v, phn kia nhng vo dung mi to thnh h keo bo v. 2.3.7.5. Hiu ng bn ca keo a nc Cc cht keo a nc c th lm bn cc sol k nc vi dung mi khc nhau nh x phng, cht ty ra. . . Cc hiu ng bn hay bo v c vai tr quan trng trong vic ch to cc h phn tn bn m ui k dung mi dnh vo ht cn lm bn, cc u phn cc quay vo dung dch. Khi ht va c tch in va b solvat ha. Cc cht khc nhau khng c bo v nh nhau, s bo v ph thuc vo i lc gia cc ht keo. Wiliam, Chang [3] thy rng i lc ca mt s cht keo vi
Bi ging CN in ho-n mn TS. L Minh c

keo vng khc vi keo cng g rubin, c ch bo v l cc ht keo k dung mi b bao bc bi cc cht a nc, lp lm bn c kch thc c phn t. Lin kt ca cht lm bn vi b mt k dung mi c th do lc hp dn Van der Waals hoc lc lin kt ion nu cu t tch in. Tng tc gia cc cu t a v k dung mi c th gy ra hin tng lm bn hay mt tnh bn gy ra s ng t. Trong trng hp ht c ph kn mt lp cht bo v th cht keo c tc dng lm bn. Trong trng hp cht keo hp ph km th bn ca ht keo gim v tc dng bo v nh, cht keo c th gy keo t theo c ch to cu ni. Nng cht keo bo v nh hng n bn keo: nng cht bo v tng th bn ca h keo tng. 2.3.7.6. S to bng ln nhau ca cc cht keo tch in H keo c th bn hay km bn khi c mt cc cht in ly v cht keo khc. ph bn h keo a nc, ngi ta c th s dng cc cht keo tch in tri du vi u phn cc ca cht keo bo v. S to bng c th xy ra khi cht keo tch in m c trn ln vi cht keo tch in dng. Khi hai cht keo tch in tri du tng tc nh vy th s to bng lun lun xy ra. Hin tng tng t xy ra khi mt cu t ca h l k nc cn cu t kia l a nc yu v c hm lng khng nhiu qu. S to bng cng xy ra khi cc cht a in ly b solvat rt km hay chng c kch thc ln v rt khng i xng. S lng v s phn b in tch cng l nhng vn quan trng trong s to bng. 2.3.8. c trng ca c ch keo t in ha cht mu S keo t xy ra do cht mu hp ph ln cc phc hydrox nhm. Cc phc hydroxo ny tip tc b thy phn, khi v nh hnh nhm hydroxit hnh thnh, cng to iu kin thun li cho cc cht mu hp ph vo. Nhm hydroxit phn t lin kt to thnh bng keo ln hn, li cun cht mu theo c ch keo t qut. Cc yu t nh hng n vic tch loi mu: -Bn cht tch mu: phng php keo t bng mui nhm ch c hiu qu i vi cc cht mu hu c phn tn, khng tan trong nc. i vi cc thuc nhum hon nguyn tan hoc hot tnh, nu cc phn t cht mu cng knh, phc tp , c

Bi ging CN in ho-n mn

TS. L Minh c

10

kh nng to phc vi nhm th phng php ng t in vn c th p dng c. y c l l hn ch p dng ca keo nhm. -Cc dng khc nhau ca keo nhm: ty thuc vo gi tr pH m cc dng tn ti ca phc hydroxo cng khc nhau. Do vy m hiu qu x l cng thay i theo gi tr pH. Khi pH= 6-8, cc ht keo nhm mang in dng, rt d tng tc vi cc cht mu mang in tch m hay trung tnh nn hiu qu x l rt cao. -Cc yu t khc nh: khuy trn dung dch, nhit . . . nh hng n tnh bn ca cc ht keo, hay ni cch khc s nh hng n hiu qu x l. Bn pha cathode, ion OH- to ra do phn ng thot kh H2 s chuyn sang anode cng vi cc phn t cht mu nhng vi tc ln hn do c kch thc b hn. Cc ion H+, hydroxo, v keo nhm s chuyn sang cathode. Ion H+ do c kch thc b hn nn chuyn ng nhanh hn cc phn t cht mu, khng tng tc trung ha in tch vi cht mu. Chng nhanh chng trung ha cc ion OH-. Cc hydroxo, keo nhm di chuyn chm hn s tham gia cc phn ng hp ph v trung ha in tch cc phn t cht mu. ng thi cc hydroxo tip tc thy phn nn tip tc hp ph, trung ha in tch cc anion mu. Cc phn t cht mu nm trong khu vc anode, s khng b tng tc va chm vi cc ion H+ nn xc sut va chm c hiu qu vi cc phc hydroxo, keo nhm l rt ln. Trong khong pH=8 , cc ion OH- ng thi tham gia phn ng thot oxy v tng tc vi H+, thc y qu trnh to phc hydroxo v keo phn tn tch in dng. Keo nhm sau khi hp ph cht mu, di tc dng tuyn ni ca cc bt kh hai cc anode v cathode s ni ln trn b mt dung dch. C ch hp ph v trung ha in tch khng ch ch yu qu trnh ng t in 2.3.9. Li ch ca phng php ng t in trong x l nc thi dt nhum Nc thi dt nhum c thnh phn phc tp do tnh cht a dng ca ha cht v cng ngh nhum. c c hiu qu cao trong x l nc thi nhum cn thit phi s dng kt hp nhiu phng php. S dng ring r cc phng php ha l, ha hc hn ch tnh u vit ca cc phng php khc. p dng phng php ng t in trong x l nc thi mang li nhng li ch sau:
Bi ging CN in ho-n mn TS. L Minh c

11

-Chi ph u t cng ngh thp. -Tiu tn nng lng thp. -Khng s dng cc ha cht b sung. -C kh nng t ng cao v di lm vic rng. -Khi nng tp cht, thnh phn trong dng thi thay i ln, ngi vn hnh h thng x l khng phi iu chnh nhiu. -Kt qu x l ng tin cy. -Lng bn gim rt nhiu so vi cc phng php khc. Thun li trong vic x l bn. -X l c nhiu loi tp cht trong dng thi. 2.3.10. Cc kt qu nghin cu ca phng php ng t in trong v ngoi nc Vit nam, cc tc gi Trng Ngc Lin (i hc Bch khoa H Ni), ng B Trinh, H Vn Khnh (Vin Ha hc) cng b nhiu cng trnh lin quan n vic ng dng phng php ng t in vi nhm, st anode ha tan x l mt s cht mu hu c. Cc l thuyt v c ch ca qu trnh cng c cc tc gi tp trung nghin cu nh bn cht ca qu trnh ng t in, cu trc ht keo nhm. . . . Song vic trin khai thc t vn cn nhiu hn ch. nc ngoi, ng t in c ng dng rng ri, a lnh vc. Di y l mt s ng dng c th: a. X l nc thi ca tu bin p dng ng t in x l nc thi ca tu bin mang li nhiu kh quan. X l nc thi c cha kim loi nng, du m, cht rn l lng nhm gim chng n mc quy nh. Vi phng php ny, c th tit kim c 150.000 USD/ tu bin trong vic x l nc thi nhim. Nc thi c th thi trc tip ra bin, chi ph gim t 75 - 90% [29]. Mt vi thng s ca nc thi sau x l ghi bng 4.1.

Bi ging CN in ho-n mn

TS. L Minh c

12

Bng 4.1 c tnh nc thi sau x l Tp cht Tng du & m Cd Pb Cu Ni Zn Toluene Xylenes Phenol Trc x l (mg/l) 2500 25 22 2,5 2,0 6,2 23 168 3,4 Sau x l (mg/l) <20 <0,01 <0,01 <0,0008 khng pht hin c <0,055 0,014 0,051 0,052

Qua nhiu nghin cu thc nghim, th nghim pilot hin trng (field pilot testing) trong x l nc thi tu bin, ngi ta thy rng phng php ng t in l rt thch hp. C th x l khi nng tp cht bin ng. b.Lm sch nc ma trn cc xa l Bng phng php ng t in, mu nc ma trn xa l King County c thu gom v x l, cc thng s th hin nh bng di y. Bng 4.2 Kt qu x l nc trn xa l King County bng phng php ng t in. Cc n v c tnh bng mg/l P tng Trc x l Sau x l 1,69 0,385 c 460 4,3 TSS 1032 3,3 FOG 7,6 <0,25 TPH 4,2 <0,25 Bari 0,228 0,008 Ch 0,0825 <0,0010

c.X l nc rc Leland G. Cole kt hp qu tnh ng t in v oxy ha x l nc rc. TSS b loi ra do qu trnh ng t in. Cc cht hu c b oxy ha v chuyn thnh cc hp cht trung gian d tch ra. Phng php ny c th p dng khi nng tp cht trong nc thi thay i ln cng nh thnh phn phc tp. d. X l nc thi nhum:
Bi ging CN in ho-n mn TS. L Minh c

13

Leland G. Cole, Jerry Kolodzik, Joseph T, Bishop nghin cu trn thit b pilot s dng phng php ng t in x l nc thi nhum. Cc i tung nghin cu y: mu, SS, kim loi nng, du m. Kt qu nghin cu: quan st bng mt thng th nc sau x l rt trong, mt mu hon ton. Trc x l COD TSS 1896 mg/l 356 mg/l Sau x l 37 mg/l Khng pht hin c

Chi ph 0,72 - 0,99 USD/1000 gallons nc x l e.Raintech International ( M) tung ra th trng thit b ng t in Powell Electrocoagulation Systems - ng dng trong x l nc thi. Mt s kt qu di y thu c khi nghin cu trong phng th nghim v thc t: Cc thng s BOD TSS (t st, than, ph sa...) Du, m, nht trong nc Nc trong bn Kim loi nng Pht pht Vi khun, virus, nguyn sinh vt Hiu sut tch % 90 99 93 - 99 50 - 80 95 - 99 93 99,99

Tnh a dng v hiu qu ca phng php ng t in cn c th thy qua cc con s bng di y. Bng 4.3: Kh nng v hiu sut x l ca phng php ng t in Tp cht BOD TSS ng Km Ngun nc thi n/cu C.bin thy sn n.thi sinh hot M in Trc x l (mg/l) 40500 5620 287 221 Sau x l (mg/l) 750 25 0,484 0,14 Hiu sut x l (%) 98,1 99,6 99,8 99,9
TS. L Minh c

Bi ging CN in ho-n mn

14

Cadimi Nhm Bari Canxi St

S/ x hp Git hi Thp lm lnh Nc thi m

31 0,30 8,0 1321 151

0,338 <0,01 <0,10 21,4 0,57

98,9 96,7 98,7 98,4 99,6

Tm li, ng dng ca phng php ng t in rt a dng, c th p dng cho nhiu loi nc thi , c thnh phn thay i ln. Bng nhng nghin cu, cc nc tin tin trn th gii p dng phng php ny mt cch c hiu qu. Cc lnh vc c th p dng phng php ny nh sau : -Lm sch nc ngm. -X l nc thi git. -X l nc cp. -X l nc thi sinh hot, cng nghip. -Tch cc ng v phng x. -X l s b cho cc qu trnh: thm thu ngc, siu lc. -Ti s dng nc thi. -Tch kim loi nng trong dng thi. -Cng ngh thc phm: ch bin sa, tht, c, nc ln men. . . .

Bi ging CN in ho-n mn

TS. L Minh c

A. IN PHN SN XUT NHM

1. Gii thiu Nhm c bit t nm 1825. Nm 1887 ngi ta sn xut Al bng phng php in phn. Sn lng Al trn th gii khong 2x107 ton/nm, in phn sn xut nhm ch ng th 2 sau in phn NaOH-Cl. Nhm l kim loi nh, bn nn c ng dng nhiu trong cng ngh. S dng nhm r tin, b mt nhm c th x l bng oxi ho to nn b mt chng n mn. Phn ln Al s dng dng hp kim vi Mg, Cu, Si, Zn, Ni, Fe. Nhng hp kim quan trng nht dura (94% Al, 4%Cu, 1,5% Mg, 0,5% Mn), silumin (hp kim c Al + 12% Si). Khng th sn xut trc tip Al t Al2O3 v Al2O3 nng chy nhit rt cao (2050oC), khng dn in. Nhm c sn xut t qung bauxite, c th cha Si, cc oxit kim loi khc c bit l st. Qung chuyn thnh nhm nguyn cht bng phn ng sau Al2O3.3H2O + 2NaOH = 2NaAlO2 + 4H2O u tin qung c x l bng NaOH, p sut cao. Nhm ho tan thnh dng aluminate, oxit st khng tan, Si cn li dng natri aluminium silicate, lm mt mt nhm. Hm lng Si cng t cng tt. Sau khi lc, oxit nhm ngm nc kt ta, NaOH c ti s dng. Al c ra sch v gia nhit 1200oC tch nc. Bc tip theo l chun b dch in phn. Nu s dng C kh Al th ch phn ng nhit rt cao. Hu ht Al c sn xut bng in phn Al nng chy vi Na3AlF6. Nhm nng chy 2020oC, to nn dung dch nng chy khng dn in. Nu ho thm 15% khi lng Na3AlF6, nhit ch 1030oC, mi trng ny s dn in. y l cng ngh ca Hall (M) v Heroult (Php).

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2. Cc yu cu i vi Al2O3 -Rt tinh khit, khng cha nhng nguyn t c in th tiu chun dng hn Al. -C hot tnh cao, tnh cht ny th hin tnh tan cao trong cryolite. Nu ho tan thp th Al2O3 lng ng xung y b. -Khng ht nc. Do mng tinh th Al2O3 khc nhau nn tinh th ht nc khc nhau. Khi nung nng Al2O3 s mt nc v mng tinh th bin i. Al2O3.3H2O 225 Al2O3.H2O 500 .Al2O3 950 .Al2O3 C C C
o o o

Al(OH)3 3. Sn xut cryolite

(AlOOH)2

.Al2O3 .Al2O3

3.1. Sn xut bng phng php acid CaF2 + H2SO4 = 2HF + CaSO4 SiO2 + 6HF = H2SiF6 + 2H2O H2SiF6 + Na2CO3 = Na2SiF6 + CO2 + H2O 12HF + Na2CO3 + 2Al(OH)3 = 2(3NaF.AlF3) + 3CO2 3.2. Sn xut bng phng php kim Bc 1: CaF2 + Na2CO3 + SiO2 = CaO.SiO2 + 2NaF + CO2 CaF2 + Na2CO3 + Fe2O3 = CaO.Fe2O3 + 2NaF + CO2 Bc 2 NaAlO2 + 2 H2O Al(OH)3 + NaOH Al(OH)3 + NaF AlF3 + NaOH AlF3 + NaF 3NaF.AlF3 Cryolite khng cha cc nguyn t c in th dng hn Al, ho tan tt Al2O3, khng tc dng ho hc vi in cc. 3.3. Mt s tnh cht ca hn hp cryolite v Al2O3

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-Hai thnh phn chnh l Al2O3 v 3NaF.AlF3, nhiu nghin cu thay bng cht khc nhng khng c kt qu. -Tnh dn in cao, nht thp, khi lng ring nhit cao nh hn Al -Trong dung dch in phn nng chy Al, thnh phn NaF v AlF3 khng phi lc no cng ph hp vi l thuyt ca cryolite, trong qu trnh in phn n gim dn. Theo chiu cao ca b in phn thnh phn ca hai cu t ny khng ng nht. T s NaF : AlF3 thng bng 3. Khi nh hn 3, dung dch c tnh acid. -Trong sn xut, lng Al2O3 thng 8%. Qu 8% Al2O3 bt u kt tinh to ra cn y b in phn. Thm AlF3, CaF2, MgF2 iu chnh cc nh hng xu. -Khi lng ring ca hn hp 1000oC : NaF : 1,961 g/cm3 Na3AlF6 : 2,112 g/ cm3 Al : 2,289 g/ cm3 Khi lng ring ca cryolite c tnh theo cng thc Klr = 2,088 0,00088 (t-1000) Khi lng ring ca Al lng Klr= 2,382 0,000273 (t- 659) 4. C ch in phn 4.1. C ch Hin c 2 c ch + ion Na+ phng in trc cathode ri t mi xy ra cc phn ng khc 2 Na3AlF6 6 NaF
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6 NaF + 2 AlF3 6 Na+ + 6 FTS. L Minh c

cathode 6 Na+ + 6 e 6 Na 6 Na + Al2O3 2 Al + 2 Na2O anode : 6 F- - 6 e 3 F 2 3 F2 + Al2O3 a Al2O3 + 1,5 O2 O2 + C 2CO O2 + C CO2 Khng gian cathode giu Na2O, vng anode giu AlF3 3 Na2O + 2 AlF3 6 NaF + Al2O3 + ion Al3+ phng in cathode Phn hu cryolite 3NaF.AlF3 Cathode : Anode : 2 AlO33- - 6 e Al2O3 + 1,5 O2 O2 + C 2 CO O2 + C CO2 Trong mi trng nng chy, c nhiu cation, anion. Chuyn n cathode c Al3+, Na+,Al+. Chuyn n anode c F-, AlF63-, O2-, AlO33-. 4.2. Cc phn ng cathode Al3+ + 3 e Al Na+ + e Na (khi mt dng in cao) Cc phn ng khc Al3+ + 3 e Al 2 Na+ + e Na2+
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3 Na+ + AlF63-

Al2O3 Al3+ + AlO33Al3+ + 3 e Al

Al+ + e Al Na2+ + e 2 Na Cc phn ng anode 2 AlO33- - 6 e Al2O3 + 1,5 O2 AlO2- - 2 e Al2O3 + 0,5 O2 4.3. Cc phn ng ph -Al cathode nng chy tan trong criolite to ra hp cht Al ho tr 1 Al + Na3AlF6 3AlF + 3NaF -Na to ra vng cathode tc dng vi dung dch in phn sinh ra NaF -To ra Al4C3 4 Al + 3C Al4C3 5. Thng in phn Hnh di l thng in phn nng chy Al t qung Al2O3 vi cryolite. Thng in phn lm bng thp khng r, bn trong bc nhm, cch nhit tt m bo khng tn tht nhit. y thng c ph bng C khi, c li l cc thanh thp gim in tr. y chnh l tip in cho cathode nhm. Hai bn thnh c ph bng than antracite.

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Th in cc tng t -4,5V n -40 - -60V do hnh thnh lp kh, F hay CF3 trn b mt anode. Thng thng gm 200 cell, tng din tch anode l 15 m2. Mt dng ti thiu l 1A/ cm2, dng tng cng l 150KA. in th in cc ph thuc vo nng Al v n s quyt nh lng cu t trong dung dch. V dng in ln, nn t trng to ra cng s ln. Dng t trng s to nn b mt tip xc pha Al/ dung dch in phn. Hiu sut dng in 85 90%. Nng lng cn thit 14000 16000 kWh / tn nhm.

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B. TINH LUYN Zn
1. L thuyt n phn tinh luyn kim loi da trn nguyn tc: in phn dung dch hoc mui nng chy ca kim loi . Thng s dng anode khng ho tan. Phn ng:

Phn ng trn anode

Dung dch in phn thng l mui sunfat ca kim loi. Acid H2SO4 c la chn v r tin. Trong nhiu qu trnh, kim loi thng cha trong qung oxit hoc sunfit vi hm lng khng ln. Vic lm giu l cn thit. in phn tinh luyn l bc sau cng. Chun b nguyn liu thng qua cc bc -Lm giu qung: tch cht thi bng tuyn ni, lm tng nng ca mui sulfit hay oxit kim loi. -Nung: chuyn kim loi dng sunfit sang dng oxit c th tan trong acid H2SO4. -C c cht tan: dung dch thu c dng sulfate, c cc tp cht khc. -Tinh ch: loi b cc tp cht c in th dng hn (c th kt ta cng vi kim loi, gim tinh khit ca kim loi, hydro phng in). Loi b cc tp cht bng cch tng pH ca dung dch, kt ta bng H2S. -in phn: kt ta kim loi ln cathhode trong thng phn ng. Khi O2 c mt anode, nng ion kim loi gim, acid ca dung dch in ly tng ln, dn n gii phng H2 ng thi vi kt ta kim loi. Thng thng phi b sung lng ion kim loi.

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2. Tinh luyn Zn Luyn Zn thng dng nht l in phn dung dch Zn sulfate. Sn phm Zn thu c c th t c 99,99%, t mt mt Cd hn cc phng php tinh luyn c in khc. Phn ng cathode, kt ta Zn:

Oxy thot ra trn in cc khng tan

Do qu th H2 trn Zn rt cao nn Zn c th kt ta trong mi trng acid vi hiu sut rt cao. Th kh ca Zn2+ m hn in th kh ca H+. C mt cc tp cht khc, chng s kt ta ng thi vi Zn. Trn cathode c nhng v tr c qu th H thp. Qu trnh thot H xy ra mnh ng thi vi ho tan Zn c kt ta (theo c ch pin cc b). Cc tp cht nh Cu, Bi, Ge v Sb khng ch lm gim hiu sut dng m cn ngn khng cho Zn kt ta. V vy mc ch x l qung Zn to ra dung dch Zn sulfate khng c tp cht, nh hng khng tt n phn ng cathode. K thut in phn Cc thnh phn c trong qung Zn nh hng n phng php x l dung dch ZnSO4. ZnSO4 tch ra theo phn ng Vi qung sulfide, cn phi nung chuyn thnh dng oxit

Tp cht trong qung Zn c chia lm 3 nhm chnh 1.Fe, Si, Al, Sb, Bi, Ge, Sn 2.Cu, Cd, Ni, Co

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3.Pb, Ag, SiO2 Khi ho tan ZnSO4, acid t do gim, pH tng. Nh vy Fe(III) s kt ta, Al v mt phn Cu dng hydroxit. Fe(OH)3 c din tch b mt ring ln, Sb, Bi v Ge s hp th ln b mt Fe(OH)3 v tch khi dung dch. As dng khng tan Fe4O5(OH)5As. Fe(OH)2 kt ta pH 6,5, ti gi tr pH ny Zn(OH)2 cng kt ta. Do vy, nn oxi ho Fe2+ thnh Fe3+.

Ni2+, Co2+ cng phn ng vi MnO2 pH thp hn, to nn ion vi ho tr 3, kt ta dng hydroxit, Co(OH)3 v NiOOH cng c tch ra mt phn. Trong qu trnh in phn, MnO2 to ra do phn ng Cc tp cht nhm th 3 s khng tan, nm trong dung dch lc ra. Kt ta cha cc tp cht nhm 1, 3 v mt phn nhm 2, tch ra bng cch lc. Tch tp cht nhm 2 b kh bi Zn bt Sau khi x l, nng Zn trong khong 120 170 g/dm3, acid t do 150200 g/dm3. Nng ion kim loi trong dung dch in ly th hin bng sau

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Vt liu cathode thng l tm Al, dy 4-8mm. Zn bm ln Al km nn d dng tch ra sau khi in phn. Anode ch dy 5-10mm, kch thc 100 x 600 mm. Thi gian lm vic 1,5 2 nm. Khi anode ch c 1-2%Ag, thi gian s dng 3-4 nm. Thi gian in phn 10 24 h, nng Zn gim xung 45 -55 d/dm3. iu kin in phn Mt dng cathode :400 700 A/m2 Hiu sut dng : 88 92% Th : 3,3 -3,6 V Nhit : 30 40 oC Tiu th in nng : 3000 3500 kWh / tn Sn xut 1 tn Zn cn : 4kg MnO2, 16 kg Zn bt, 62 kg H2SO4.

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C. TINH LUYN Cu
1. L thuyt ng sn xut bng cc qu trnh luyn kim cha nhiu tp cht, thng 0,5 2%. Tp cht nh hng xu n tnh cht c, in ca Cu. 0,15% P hoc 0,5 % As s gim ng k dn in. V vy, ci thin tnh cht in ca Cu l l do chnh ca in phn tinh luyn. L do th 2 ca tnh luyn in ho l tch cc kim loi qu nh Au, Ag, Pt, Pd . . .

Cc tp cht c chia lm cc nhm 1.Ni, Co, Fe, Sn, Zn, Pb 2.Cu2O, Cu2S, Cu2Se, Cu2Te 3.Au, Ag, Pt, Pd, Se, Te 4.As, Sb, Bi Cc phn ng chnh in cc

Tp cht nhm 1: th in cc m hn ca Cu, s ho tan cng vi Cu, chuyn vo dung dch. Do c anion sulfate trong dung dch nn ch sulfate to nn bn ca anode. Cc kim loi khc nh Ni, Co, Sn v Zn s tch lu trong dung dch, v th ca n m hn th ca cathode. Tuy khng c nh hng xu nhng cn phi nh k tch chng ra khi dung dch. Ion Fe2+ do ho tan

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anode to ra, nhng s khng kt ta do th m hn so vi th ca cathode. T phng trnh Nernst

th ph thuc vo t s Fe2+ / Fe3+. Nu nng Fe3+ thp hn Fe2+, in th cn bng s m hn in th anode, Fe2+ b oxi ho thnh Fe3+. Nng Fe2+ gim, nng Fe3+ li tng. Fe3+ li b kh thnh Fe2+ ti cathode. Nu hai phn ng ny xy ra s tiu hao nng lng in ca c qu trnh. Cc tp cht khng tan ca nhm th 2 nh Cu2S, Cu2Se, Cu2Te khng b ho tan anode nhng sa lng, to bn anode. Ch Cu2O c th b ho tan theo phn ng V th, mt na lng Cu b ho tan trong dung dch in ly dng ion Cu2+, mt na kia to thnh bt mn, c th phn ng vi O2 v H2SO4, mt t to mn anode. Kim loi nhm 3 nh Au, Ag, Pt, Se v Te cng to mn anode. Chng bn hn Cu, khng tan v hnh thnh mn anode. Cc tp cht nhm 4 nh As, Sb, Bi lm gim ng k cht lng ca Cu cathode. Chng kh tch v th in cc xp x vi Cu, nm gia th ca H v Cu. Tuy nhin, nng ca chng nh do vy, th kt ta m hn so vi th ca cathode. Trong mt iu kin no y, chng khng b kt ta. Khi nng ion Cu gim, n kh kt ta. Mc khc, Sb, Bi c th phn ng vi As tp mun arsenate tan, to bt mn trn dung dch, lm kh khn trong thao tc.

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2. K thut in phn Anode Cu 99 95%. Din tch khong 1 1,5 m2, rng 40 50 mm, khi lng 300 350 kg. Anode dy 1mm, nng 5 kg. S lng in cc ph thuc nng sut ca nh my.

iu kin in phn -Mt dng cathode :200 300 A/m2 -Hiu sut dng : 94 96 % -in th : 0,25 0,35 V

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-Nhit : 55 -60 oC -Nng lng tiu hao : 250 360 kWh/t Sau in phn, cathode Cu t 99,97 99,99 %.

Trong qu trnh in phn, dung dch s tch lu dn Ni, Sb, As. Cc tp cht ny s ly ra trong giai on ti sinh. Bn anode chuyn i x l tip. in phn tinh luyn Cu l mt qu trnh in ho, v l thuyt thnh phn ca dch in phn khng thay i trong qu trnh. Nhng thc t l c bin i. Trc ht, dch in phn acid s ho tan mt lng Cu anode khi c O2, iu ny s lm tng nng ion Cu2+, nng acid t do s gim. Th 2, tp cht trong anode Cu khng i vo bn m lu li trong dung dch, gp phn lm gim nng acid t do.

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3. iu chnh dung dch Thc t c 2 cch hiu chnh thnh phn v lm giu dung dch. Cc th 1 bao gm vic tch loi Cu, As v Sb bng kt ta cathode trong mt thng in phn khc vi anode khng ho tan. Qu trnh ny lm tng nng acid t do sau khi dung dch c c c, ti y Ni, Fe v Cu sulfate s kt tinh. Phng php th 2 : trung ho acid H2SO4 t do bng qu trnh ho tan Cu. Cu sulfate s kt tinh trong dung dch bo ho. Dung dch cn li mang i in phn trong thng c mng ngn tch Cu, As v Sb. Tch Ni, Zn, Fe bng c c. Sau tinh luyn, dung dch in phn thng ch c acid sulfuric, tip tc hiu chnh dung dch bng qu trnh ho tan Cu. X l mn anode Mn anode cha nhiu kim loi qu him, hp kim nh nhm Pt, Au,Ag, Se, Te, . . Cu tch ra khi mn, ho tan trong H2SO4 long nng, c khng kh, sau , Se v Te c tch ra. Tip theo, sau khi thm natri cacbonat, natri nitrat, ct thch anh, mn c nng chy to nn hp kim 93% Ag, 3% Au, 1% Cu, 0,05% Pd, 0,03% Pt, cc kim loi vt khc. Ag vi tinh khit 99,99% c tch ra khi hp kim bng qu trnh ho tan anode trong dung dch Ag nitrate. Do mt dng trao i cao nn Ag kt ta ln in cc vi bm dnh rt km, cu trc thng in phn tinh luyn c cu trc c bit thu mn anode. Sau x l tinh luyn Ag, mn anode cha 95% Au, 5% Ag, 1% Cu, Pd, Pt v cc kim loi khc. Sau khi nng chy v cn tm, anode a vo b in phn, dung dch HAuCl4 v acid HCl t do. in th kt ta Au cao 1,4V, tt c cc tp cht tr Ag dng AgCl, s b ho tan v lu li trong dung dch.

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Khi lng Pt, Pd t c 75 g/dm3, dung dch cn thay th. Cc kim loi ny thu hi dng mui ammonium ; (NH4)PdCl6, (NH4)2PtCl6. Kh cc mui kim loi ny, thu c Pd v Pt.

Ti liu tham kho [1]. Konstantin I. Popov, Branimir N. Grgur , Stojan S. Djokic, Fundamental aspects of electrometallurgy, 2002. [2]. D. Pletcher, F. C. Walsh, Industrial Electrochemistry, 1993. [3]. V. S. Bagotsky, Fundamentals of Electrochemistry, 2006. [4]. C. M. A.Brett, A.M. O.Brett, Electrochemistry-Principles, Methods and Applications, 1993.

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