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n mn v bo v kim loi
Trnh Xun Sn
T kho: n mn kim loi, Phn ng n mn, Faraday, Pin in ha, Bnh in phn, dn
in, Linh ion, S vn ti, Dung dch cht in ly, o dn in, n mn v bo v kim
loi, Th in cc, Sc in ng ca bin in, in cc, Lp in kp, Sc in ng. n
mn, Kim loi, Tc n mn.
Mc lc
Chng 1
Phn m u
Trong qu trnh xy ra hin tng n mn in ho lun lun xut hin phn ng anot v
phn ng catot gn lin vi s trao i electron ca phn ng oxi ho. Dng electron ny
c truyn t anot sang catot v sinh ra dng in.
V mt in ho th mt phn ng in ho xy ra l s bin i ho hc gn lin vi s
chuyn in tch trn mt gii hn ca hai pha tip xc l cht dn in loi mt, dn in
electron v cht dn in loi hai, dung dch cht in li. Mt phn ng in ho c th bao
gm mt hoc nhiu phn ng in cc. Vy phn ng n mn (1.3) cng l mt phn ng
in ho, trong nguyn t st chuyn thnh ion Fe2+ i vo dung dch km theo s trao i
hai electron trn b mt kim loi vi cc proton H+ trong dung dch. N gm hai phn ng
in cc: s oxi ho st v s kh cc proton.
Theo nh ngha trn th tt c cc phn ng n mn dn n s oxi ho kim loi (kim
loi tip xc vi dung dch cht in li) u l cc phn ng in ho.
A
O2
H2
Hnh 1.1
Pin hiro oxi
1. Dung dch axit H3PO4 hoc H2SO4;
H2 O2
2 1
Hnh 1.2
Bnh in phun nc iu ch H2 v O2
2
1 b
a
S kh
S oxi ho
11
Hnh 1.3
S n mn ng u (a) v n mn nh x (n mn vng) (b)
1. Kim loi ; 2. Mi trng n mn
S kh S oxi ho
H2
Fe Pt
Hnh 1.4
a b
c d
e f
g h
Hnh 1.5
Cc dng n mn thng gp trong thc t
14
Chng 2
1.4 M u
Dung dch cht in li cn gi l cht dn in loi hai, s dn in ca n nh s ti
in ca cc ion. Kim loi v oxit kim loi dn in bng electron c gi l cht dn in
loi 1 v c in tr khong 106 103 .cm.
Nghin cu v dn in ca dung dch cht in li c lin quan cht ch vi hin
tng n mn in ho v cho php gii thch s khc bit v tc n mn trong mi trng
nc bin v nc sng, ao, h.
nh gi kh nng dn in ca dung dch cht in li ngi ta s dng hai i lng:
dn in ring v dn in ng lng ca dung dch cht in li.
2.2.2 dn in ng lng
Hnh 2.1
S ph thuc ca dn in ng lng vo pha long V
16
Hnh 2.2
S di chuyn ca cc ion di tc dng ca in trng
NA - l s Avogaro.
Nu gi Q l in lng do cation v anion ti th:
Q = + Z+ . e + Z . e (2.15)
trong : Z+, Z l s oxi ho ca cation v anion;
e l in tch c bn, e = 1,602.1019C.
i vi cht in li 1-1, Z1 = Z = 1
hoc Q = C NA e.103.E (+ Z+ Uo + Z Vo) (2.16)
Dung dch cht in li lun trung ho in nn + Z+ = Z = Z
Vy phng trnh (2.16) c dng:
Q = i = 103 C F Z (Uo + Vo)E (2.17)
y lng in Q do ion ti trong mt n v thi gian i qua 1 cm2 chnh l cng
dng in i i qua ng dung dch (hnh 2.2).
Tng t i vi dy dn kim loi c in tr R c dng in i i qua dy dn v in th
E, i vi ng dung dch cht in li (hnh 2.2), theo nh lut m ta c:
i = .E (2.18)
So snh (2.17) v (2.18) rt ra:
= 103 C F Z (Uo + Vo) (2.19)
Mt khc, ta c:
1000.
= = F (Uo + Vo) (2.20)
Cd lg/ l
426,00 91,00 126,50
( .cm2.lg1)
1
H H H +
H
+
H O H + O H H O + H O H
Zn
Cation H3+ O Na+ K+ NH4+ Ca2+ 2+
Gi tr linh
349,8 50,1 73,5 73,5 59,5 52,8
V (25oC)
Gi tr linh
197,6 55,4 67,3 64,6 80
V (25oC)
i vi ion OH
H H H H
O + H O O H + O
Nng H+
Dung mi 25oC Nhit
25oC
Trong dung mi nc
Hnh 2.3
S ph thuc ca dn in ring vo nng C
Hnh 2.4
S ph thuc ca dn ng lng vo nng C
Hnh 2.5
1.9 S vn ti
Khi dng in mt chiu i qua dung dch cht in li, trn catot xy ra phn ng phng
in ca cc cation v trn anot cc anion nhng in t hoc c s ho tan kim loi. Hin
tng gi l s in phn.
Theo nh lut Faraday, lng cht c thot ra hoc b mt i trn cc in cc trong
qu trnh in phn t l vi lng in i qua bnh in phn cng nh t l vi ng lng
ho hc ca cc cht.
c c mt ng lng gam cht thot ra hoc mt i trn cc in cc cn phi c
mt Faraday (96493 C) - 1 F in lng i qua bnh in phn.
Biu thc nh lng ca nh lut Faraday:
g I.t
= = (2.34)
a 96493
trong :
23
Hnh 2.6
S cc khu vc ca bnh in phn ng vi s bin i nng khi t s tc chuyn ng tuyt
24
i Uo/Vo = 2/3
1. Trng thi trc in phn;
2. Trng thi sau in phn
Trc khi in phn nng hai khu catot v anot bng nhau (mi du +, th hin phn
ng lng gam, v d 0,01 lg).
Uo 2
Gi thit tc tuyt i cation Uo v anion Vo l = , ngha l khi xy ra in phn
Vo 3
c 0,01 2 ng lng gam cation c chuyn n catot, ngc li c 0,01 3 ng
lng gam anion c chuyn n anot (xem hnh 2.4, trng thi 2). Nhng ion khng cp i
tham gia phng in v tng s ng lng cation v anion phng in trn catot v anot
u bng:
0,03 + 0,02 = 0,05 lg = n
Gi na v nc l gin nng ng lng ca cht in li ti khu anot v khu catot
sau in phn, ta c:
n a Uo 0,01.2 2
= = = (2.39)
n c Vo 0,01.3 3
Mt khc:
n = na + nc (2.40)
T (2.39) v (2.40) ta c:
Uo n a
t+ = =
U o + Vo n
Uo n c
v t = = (2.41)
U o + Vo n
T (2.41) rt ra:
S ti cation t+ bng t s gim nng ti anot (na) so vi gim lng cht ca
ton b (n) qu trnh in phn, mt cch tng t s ti anion t chnh bng t s gim
nng ti khu catot (nc) so vi gim lng cht ca ton b qu trnh in phn (n).
Trong mt s trng hp s ti cation t+ bng t s gim nng ti khu catot (nc) v
s ti anion t bng t s gim nng ti khu anot (na) so vi gim lng cht ca
ton b qu trnh in phn (n). V d tnh s ti t+ v t i vi qu trnh in phn dung
dch NaOH v H2SO4.
S hiu bit v s ti c ngha nht nh i vi l thuyt dung dch cht in li, cho
php tnh c gi tr dn in ca ion theo cng thc:
+ = .t+ (2.42)
- dn in ng lng ca phn t nng v cng long.
25
Hnh 2.7
S mch o dn in ca dung dch cht in li
R1
Cc in tr R1 v R2 c chn trc c = 1. iu chnh RM sao cho khng c
R2
dng in i qua CD. Khi ng h G ch s khng (hoc dng ng nghe c gi tr nh
nht). Khi cu cn bng ta c:
I1 RM = I2 R1
v I1 Rx = I2 R2
RM R1
Vy = = 1 RM = Rx
Rx R2
A
K= [cm1] gi l hng s bnh.
S
Rx c xc nh bng thc nghim, bit hng s K l tnh c .
26
Hnh 2.8
ng cong chun dn in k
AOB - chun axit HCl bng dung dch NaOH;
AOB - chun axit yu bng baz mnh; V - im tng ng
Chng 3
Th in cc v sc in ng ca pin in
3.2 Lp in kp trn b mt in cc
Khi nhng mt kim loi Me vo trong dung dch mui cha ion Men+ ca n (v d nhng
kim loi bc vo dung dch AgNO3 long, kim loi ng trong dung dch CuSO4) trn b
mt gii hn xy ra hin tng chuyn ion kim loi t kim loi vo dung dch.
Ta xt trng hp kim loi bc trong dung dch AgNO3 long (hnh 3.1).
29
Hnh 3.1
S hnh thnh lp in kp trn mt gii hn pha
ca in cc Ag trong dung dch AgNO3 long
Hnh 3.2
a) Lp kp c tnh n chuyn ng nhit;
b) S phn b th E(V) theo chiu dy lp kp
U = C SP (3.5)
trong : C: Tng ha th ca cc cht u tham gia phn ng;
SP: Tng ha th ca cc cht sn phm c to ra.
Ta c: U = Cu2 + + 2e Cu
U = Cu
o
2 + + RTln a
Cu2 +
+ e Cu
U = Cu 2 + + 2e Cu + RTln a = ZFE
o
Cu2 +
Vy th in cc E bng:
Cu
o
2 + + 2 e Cu RT
E= + lg aCu2 +
ZF ZF
RT
E = Eo + lg aCu2 + (3.6)
ZF
o Cu
o
2 + + 2 e Cu
trong : E = gi l th in cc tiu chun ( 25oC).
ZF
o
Vy: E = E khi hot aCu2 + = 1.
Phng trnh (3.6) gi l phng trnh Nernst. Cn ch rng bng con ng l thuyt
v thc nghim khng xc nh trc tip c gi tr tuyt i ca th in cc tiu chun Eo.
Phng trnh Nernst vit cho phn ng tng qut (3.1) nh sau:
i
o RT a oxi
E=E + ln i
(3.7)
ZF a Re di
hoc 25oC ta c:
i
0,059 a oxi
E = Eo + lg i
(3.8)
Z a Re di
Thng thng hot kim loi tham gia phn ng c quy c bng n v (tr trng
hp kim loi trong hn hng thy ngn), hoc hot ca nc bng n v.
i vi cht kh thay cho vic biu din nng ngi ta dng khi nim p sut v d
PO2 , PH2 ...
0,059
hoc EFe2 + = 0,441 + lg 10 6 = 0,618 V
Fe 2
3.4.1 in cc loi 1
33
0,059
EZn2 + = 0,76 + lg a Zn2 +
Zn 2
V d 2: Cu2+/Cu hoc (CuSO4/Cu) vi phn ng in cc:
Cu2+ + 2e U Cu
0,059 aCu2 +
25oC ta c: ECu2 + = ECu
o
2+ + lg
Cu Cu 2 aCu
0,059
ECu2 + = 0,34 + lg aCu2 +
Cu 2
V d 3: Fe2+/Fe hoc (FeSO4/Fe) vi phn ng in cc:
Fe2+ + 2e U Fe
0,059 aFe2 +
25oC ta c: EFe2 + = EFe
o
2+ + lg
Fe Fe 2 aFe
0,059
EFe2 + = 0,441 + lg aFe2 +
Fe 2
Cc in cc kim loi trong hn hng tip xc vi dung dch mui ca n cng thuc vo
in cc loi 1.
3.4.2 in cc loi 2
in cc loi 2 l in cc lm vic thun nghch vi anion. Thng thng in cc loi
ny gm kim loi nhng vo dung dch mui t tan ca n.
V d: in cc bc Cl / AgCl / Ag c phn ng in cc l:
Ag+ + e U Ag hoc AgCl + e U Ag + Cl
Ta thy rng nng Ag+ rt nh v mui AgCl rt t tan v bng:
34
TAgCl
C Ag =
CCl
0,059
EAgCl = EoAgCl + lg TAgCl 0,059 lg CCl (3.11)
Ag Ag 1
0,059
trong : EoAgCl = EoAg + + lg TAgCl
Ag Ag 1
in cc Gi tr th (V) v NHE
5 8
6
4 5
3 4
3
2
2
1 7
6 1
Cu to in cc bc S in cc calomen
1. Dung dch HCl; 2. Mui AgCl; 1. L xp; 2. L xp; 3. Hg2Cl2;
3.4.3 in cc kh
Thng thng cc in cc kh gm kim loi tr, v d platin c din tch rt rng hp
th kh, kh tip xc vi dung dch cht in li c cha ion ca nguyn t dng kh. Vic
nghin cu cc in cc kh hiro v oxi rt c ngha i vi vic gii thch n mn in
ha ca kim loi trong cc mi trng cht in li, chng ta s ln lt xt cc in cc kh
hiro v oxi.
1
H2
H2
Hnh 3.5
S in cc kh hiro
3. Cu ni
0,059 a2H+
E2H+ = o
E2H + + lg (3.15)
H2 H2 2 PH2
E2H+ = E2H
o
+ = 0,0000 V
H2 H2
hoc t rH = lg PH2 ta c:
i vi phn ng (3.19):
o
EO 2
H2O
(
= 1,229 + 0,059 lg aH+ .PO2
1/4
) (3.21)
38
Hai phng trnh (3.20) v (3.21) l tng ng nhau nu thay th hot OH aH2 =
KW 10 14
= ; nu t lg PO2 = rO th cc phng trnh (3.20) v (3.21) c dng:
a H+ a H+
0,059 aFe3 +
hoc EFe3 + = 0,771 + lg (3.23)
Fe 2+ 1 aFe2 +
4
Mn2 +
4
Mn2 +
5 a Mn2 + .a4H2O
a MnO
hoc EMnO ,H+ = 1,507 0,0945pH + 0,0118 lg 4
4
Mn2 +
a Mn2 + .a4H2O
Phn ng in cc:
MexOy + yH2O +2ye U xMe + 2yOH (3.26)
Loi in cc ny thng xy ra trong qu trnh to mng th ng kim loi.
V d 1: in cc oxit antimon c cng thc: Sb2O3/Sb, OH trn b mt c ph lp
Sb2O3 hoc lp Sb(OH)3.
Phn ng in cc:
Sb2O3 + 6e + 3H2O U 2Sb + 6OH
Phng trnh Nernst tnh th in cc ca in cc ny 25oC l:
ESb2O3 = ESb
o
2O3
0,059 lg aOH (3.27)
Sb,OH Sb,OH
ESb O + = ESb
o
O .H+
0,059pH (3.28)
2 3 .H 2 3
Sb Sb
Nu aHgO = 1, aHg = 1 th ta c:
EHgO = EHgO
o
0,059 lg aOH (3.29)
Hg,OH Hg,OH
v Fe3+ + e U Fe2+
Vi th cn bng 25oC bng:
aFe3 +
EFe3 + = 0,77 + 0,059 lg (3.31)
Fe2 + aFe2 +
Sau khi trn hai h oxi ho kh trn vo nhau v phn ng t trng thi cn bng nu
cc phng trnh (3.30) v (3.31) bng nhau:
aCe4 + aFe3 +
1,61 + 0,059 lg = 0,77 + 0,059 lg
aCe3 + aFe2 +
Kcb rt ln, ngha l phn ng xy ra vi nng cht to thnh CCe3 + v CFe3 + rt ln.
Vy phn ng xy ra theo hng oxi ho ion Fe2+ thnh Fe3+ v kh ion Ce4+ thnh ion Ce3+.
Ta cng c th ly v d khc xt chiu hng phn ng xy ra khi cho kim loi hot
ng phn ng vi dung dch mui y kim loi km hot ng ra khi mui. V d nhng
kim loi st vo dung dch CuSO4. Cc phn ng xy ra 25oC:
Fe2+ + 2e U Fe
0,059
EFe2 + = 0,4402 + lg aFe2 + (3.32)
Fe 2
Cu2+ + 2e U Cu
0,059
ECu2 + = 0,3370 + lg aCu2 + (3.33)
Cu 2
41
Hng s cn bng rt ln, vy phn ng xy ra theo chiu kim loi st chuyn thnh ion
Fe v ion Cu2+ chuyn thnh ng kim loi mt cc hon ton, ngha l nu hot ca ion
2+
Fe2+ = 1 th hot ca ion Cu2+ = 1026, khi trong dung dch nng ion Cu2+ rt nh.
Tt c nhng nguyn t dng kh trong dy th oxi ha kh c in th m hn th
in cc tiu chun hiro u khng bn nhit ng hc khi tip xc vi nc.
V d 1 : Kim loi Na trong cp oxi ha kh Na+/Na c o
ENa + = 2,71 V, khi
Na
cho vo nc s phn hy nc gii phng hiro:
1
Na + HOH = Na+ + OH + H2
2
V d 2: Cho Ti2+ trong cp oxi ha kh Ti3+/Ti2+ vi EoTi3 + = 0,37 V, khi
2+
Ti
cho vo nc s phn hy nc gii phng hiro:
1
Ti2+ + HOH = Ti3+ +OH + H2
2
Tt c nhng in cc c th in cc tiu chun m hn so vi th in cc oxi u
khng bn nhit ng hc khi chng tip xc vi oxi v nc, dn n chng s d dng kh
oxi, v d kim loi st tc dng vi oxi trong khng kh theo phn ng:
1
Fe + O2 + H2O = Fe2+ + 2OH ( EFe
o
2+ = 0,44 V)
2 Fe
1
hoc Cu + O2 + H2O = Cu2+ + 2OH ( ECu
o
2+ = 0,34 V)
2 Cu
mt nhit ng hc v lm phn hy nc gii phng oxi. V d trong dung dch cha ion
Ce4+ ( ECe
o
4+ = 1,61 V) d dng chuyn thnh ion Ce3+ v gii phng hiro theo phn ng:
Ce3 +
1 1
Ce4+ + H2O = Ce3+ + H+ + O2
2 4
nh gi bn nhit ng hc ca cc in cc trong dung dch nc ngi ta dng
gin th - pH (xem phn tip theo) ca Poubaix.
42
Go3
Fe Fe3+
3e
2e 1e
Go2 Go1
Fe2+
Hnh 3.6
S pin in Danien - Jacobi (pin ng km)
1. Dung dch ZnSO4; 1. Dung dch CuSO4; 2,2. Km v ng kim loi;
3. Cu ni 2 dung dch (cu aga); 4. Ampe k
Khi khp kn mch bng dy dn loi 1 (dy ng) pin s hot ng v c ch th qua
ng h ampe, trn hai in cc xy ra cc phn ng sau:
Trn anot (): Zn 2e Zn2+ ; EoZn2 + = 0,76 V
Zn
3.6.2 Sc in ng ca pin in
Bin thin th ng nhit ng p ca phn ng (3.34) v cng in ca pin Danien -
Jacobi c quan h vi nhau theo phng trnh:
G = AMax = ZF (3.35)
trong : AMax l cng cc i hu ch; sc n ng ca pin in; F hng
s Faraday (96493 C); Z s electron trao i.
Theo quy c, sc in ng ca pin in c tnh theo cng thc sau:
= E+ E (3.36)
trong : E+ th in cc dng; E th in cc m.
T phng trnh 3.34, da vo bin thin ho th c quan h vi sc in ng ca pin
in rt ra c cng thc tnh sc in ng ph thuc vo nng cc cht phn ng xy
ra trong pin.
Vy:
RT a Zn .aCu2 +
= o + lg (3.37)
ZF a Zn2 + .aCu
44
Phn ng 25oC th ta c:
0,059 a Zn .aCu2 +
= o + lg
Z a Zn2 + .aCu
o RT a Re2 d .aOx
1
Vy = + lg 2 1
(3.38)
1'
.a Re2 d
'
ZF aOx
2 1
RT
= o lg a CdSO4 (3.42)
F
Vi dung dch CdSO4 bo ho, gi tr s ca pin bng 1,018 V, gi tr ny rt n nh v
ph thuc vo nhit :
= 1,018 4.105(t 20oC) V
Cc cquy axit, cquy kim c xp vo loi pin ha hc n gin.
b) Pin ho hc phc tp
Pin ho hc phc tp l mt h in ho gm hai in cc loi 1 khc nhau ghp li. V
d Pin Danien - Jacobi.
S pin: () Zn / ZnSO4 // CuSO4 / Cu (+)
Khp kn mch xy ra phn ng tng cng:
Cu2+ + Zn U Cu + Zn2+ (3.43)
Trong n mn in ho thng tn ti loi pin ny khi c hai kim loi tip xc vi nhau
c t trong mi trng cht in li (s nghin cu phn sau).
i vi pin Pin Danien - Jacobi sc in ng c tnh:
0,0591 a Cu2+
= o + lg
2 a Zn2+
0,0591 a Cu2+
= 1,1 + lg
2 a Zn2+
Khi pin nm trng thi cn bng th hng s cn bng Kcb ca phn ng c tnh:
0,0591
1,1 = lgKcb
2
Suy ra: Kcb = 1037 ngha l khi a Zn2 + = 1 th aCu2 + = 1037, khi nng ion Cu2+ rt
nh v km hon ton b n mn, qu trnh ho tan km y xy ra mt cch t din bin.
2. Pin nng
46
a2
= 0,0591lg
a1
a2
Khi nng = 10 th sc in ng E = 0,0591 (V).
a1
cquy AB
x AK
acquy AB
Vy: =
E AK
Hnh 3.7
S cu b chnh o sc in ng pin in
cquy: Sc in ng cquy; AB: Dy in tr u; x: Sc in ng pin o;
w: Sc in ng pin chun; G: in k; K: Con chy tip xc;
K: Con chy tip xc; O: Tip xc ng ngt in
Rt ra:
AB
x = cquy. (a)
AK
V gi tr in ng cquy khng hon ton chnh xc nn phi chnh li gi tr cquy bng
pin chun Weston c gi tr w = 1,018 V. Gi tr ny khng thay i theo v tr song c thay
i theo nhit v kh nng phc hi ca pin ny rt nhanh.
Tng t trng hp xc nh, thay x bng w (xem hnh 3.7) v m tip xc O, ta li di
chuyn con chy K, tm v tr ng vi in k G ch s khng v d im K, ta c:
cquy AB ; w = AK.
AB AB
Ta c: cquy = w. . (b)
AK AK '
Kt hp hai cng thc (a) v (b) ta c:
AB AK AK
x = w. . = 1,018. (V)
AK ' AB AK '
Vy ta ch cn xc nh AK v AK l o c sc in ng E ca pin in. Ch : c
th thay dy in tr u AB bng cc hp in tr.
48
Vy: G = H T2F (3.47)
T p
hoc: 2Fo = H T2F
T p
H
v o = +T (3.48)
2F T p
trong Qp gi l nhit phn ng. Phng trnh (3.49) cho bit quan h gia sc in
ng v nhit phn ng.
49
Nu = 0 th ton b nhit phn ng chuyn thnh cng in v < 0 th ch
T p T p
c mt phn nhit phn ng chuyn thnh cng in, trong mt phn chuyn cho mi
trng. Vy khi pin lm vic th mi trng xung quanh nng ln.
Nu > 0 th cng in thu c ln hn nhit phn ng chuyn thnh cng.
T p
sinh cng in, pin lm vic thu nhit ca mi trng, v th khi pin lm vic mi trng s b
gim nhit .
Mt v d khc, o sc in ng pin in tnh pHx ca mi trng.
Mun o sc in ng tnh pHx ca mi trng ta phi chn hai in cc to ra pin:
+ 1 in cc so snh (in cc bc hoc Calomen)
+ 1 in cc ch th Hx+ (in cc hiro hoc in cc thu tinh, in cc oxi ho kh
quinon v hiroquinon). y ta chn in cc hiro 2Hx+ / H2 (Pt), vi PH2 = 1 atm.
Chng 4
Gin th in cc -pH
4.1 M u
Gin th in cc - pH trnh by s ph thuc ca gi tr th in cc vo gi tr pH
ca mi trng phn ng. Gin ny c xy dng trn c s cc s liu nhit ng hc v
cho php gii thch trng thi tn ti, tnh cht ca n cht v hp cht cng nh kh nng
chuyn ho gia cc cht c trong h kho st.
S n mn kim loi theo c ch in ho xy ra trong mi trng nc lun gn lin vi
hai qu trnh: s oxi ho kim loi ti anot chuyn kim loi thnh ion kim loi v lun gn lin
vi phn ng kh xy ra trn catot - s kh ion H3+ O c trong dung dch hoc kh oxi ho tan
trong dung dch hoc kh nc.
Mt khc, s n mn kim loi theo c ch in ho ph thuc vo gi tr th in cc ca
anot v catot. Trong mi trng nc cc gi tr th in cc c ph thuc vo pH. V vy
vic xy dng gin th in cc cn bng - pH l cn thit v gi tt l gin th in
cc - pH (E - pH).
M. Pourbaix l ngi u tin a ra gin ny (1945) v cn gi l gin M.
Pourbaix.
0,059 aFe3+
i vi (4.1): EFe3+ / Fe2+ = Eo + lg
1 aFe2+
0,059 aFe3+
hoc: EFe3+ / Fe2+ = 0,77 + lg (4.3)
1 aFe2+
aFe3+
Khi t s = 1 th EFe3+ / Fe2+ = Eo = 0,77 V (SHE).
aFe2+
Hnh 4.1
S ph thuc ca gi tr th in cc E v pH (E - pH)
a) i vi h oxi ho kh thun tu; b) i vi h axit - baz thun tu;
c) i vi h hn hp ca (a) v (b).
azH+ = K. aMez+
1 1
Vy: pH = lg (4.6)
n K.a Mez +
1 1 1 1
v pH = lg 8
+ lg
2 1,45.10 2 a Cu2 +
1 1
pH = lg1,45.108 lg a Cu2 + , khi a Cu 2 + = 1; pH = 3,9
2 2
T phng trnh (4.6) cho thy gi tr pH ca phn ng (4.5) khng ph thuc vo th
in cc. Trn gin E - pH (hnh 4.1) h on thng song song vi trc tung th hin pH
khng ph thuc th in cc.
zF /j
a / .a m /2
H 2O
j
RT RT
E = Eo lnK 2,303 .m.pH
zF zF
hoc E = a bpH
(4.9)
RT RT
trong : a = Eo lnK v b = 2,303 .m
zF zF
m
25oC ta c: b = 0,059
z
53
m
i vi phn ng (4.8) h s b = 0,059 ( 25oC).
n
T phng trnh (4.9) gi tr th in cc phc thuc vo pH v trn th E - pH (hnh
m
4.1c) quan h c th hin bng h on thng c dc b = 0,059 .
z
o 0,059 a 2H+
25 C: E2H+ /H = E2H
o
+
/H
+ lg
2 2 2 PH2
Hnh 4.2
Khi PH2 > 1 atm on thng OA dch chuyn v pha m ng vi O1A1 v s kh ion H+
chim u th, phn ng dch chuyn v pha phi. Ngc li, khi PH2 < 1 th on OA dch
chuyn v pha dng ng vi on thng O2A2, kh nng gii phng H2 b hn ch, nc
trng thi bn vng.
S c mt ca oxi ng vai tr rt quan trng trong n mn kim loi mi trng trung
tnh. Trong trng hp ny s ho tan ca kim loi thp xy ra trn anot lun gn lin vi
phn ng catot - s tiu th oxi theo phn ng:
O2 + 4e + 4H+ U 2H2O (4.14)
hoc O2 + 4e + 2H2O U 4OH (4.15)
Phn ng (4.14) xy ra trn in cc oxi, th in cc c tnh theo phng trnh Nernst
v c gi tr sau:
0,059
25oC: E O2 / H 2 O = o
EO 2 / H2 O
+ lg a 4H+ . PO2 (4.16)
4
0,059
hoc: EO2 / H2O = 1,228 V 0,059pH + lg PO2 (4.17)
4
Khi PO2 = 1 atm, s ph thuc ca th in cc vo pH theo (4.17) c th hin trn
hnh 4.2 ng vi on thng BC.
55
Nu PO2 > 1 atm on thng BC dch chuyn v pha dng ng vi B2C2, phn ng
(4.14) dch chuyn v pha tri chim u th ngha l d dng phn hu nc thnh oxi.
Ngc li, khi PO2 < 1 atm th ic cc dch chuyn v pha m ng vi ng B1C1, s
phn hu nc thnh oxi din ra rt kh khn.
Ta c th ni rng trong vng din tch BCAO nc trng thi bn vng.
0,059 CFe3 +
o
EFe 3+
/ Fe2 +
= 0,77 + lg = + 0,77 V
1 CFe2 +
E = EFe(OH)
o
2 / Fe
+ 0, 059 lg C2H+ (4.24a)
2
Mt khc, phng trnh (4.24) c th vit dng khc vi nng Fe2+ rt b.
Fe2+ + 2e U Fe, tch s tan Fe(OH) TFe(OH)2 = 1,9.1035.
Vy: E = EFe
o
2+
/ Fe
+ 0, 059 lg CFe2 + , nng CFe2 + rt b.
2
Hnh 4.3
Gin th - pH i vi h Fe - H2O 25oC, P = 1 atm
ng vi th oxi ha kh 25oC:
0,059
E = 1,676 + lg C Al3 +
3
6
Vi C Al3 + = 10 M th E = 1,794 V (4.28a)
0,059
E = 1,2 + lg C( AlOH) 0,079pH
3 4
6
Vi C Al(OH) = 10 M th pH = 10,53 (4.32a)
4
Hnh 4.4
4.3.2.3 Gin th E - pH ca km
+
ZnO2 + 4H + 2e U Zn + 2 H2O (4.35)
Th cn bng:
o 0,059
E ZnO / Zn = E + lg C ZnO . C2H+
2 2 2
o
E ZnO / Zn = E 0,118pH + 0,0295lg C ZnO (4.35a)
2 2
Trong min kim thp ion Zn2+ b chuyn thnh Zn(OH)2 theo phn ng:
Zn2+ + 2H2O U Zn(OH)2 + 2H+ (4.36)
vi hng s Kcb = 7.58.1010
Vy lgKcb = lg7,58.1010 = 2lg CH+ lg C Zn 2 +
Hnh 4.5
Gin th E(V) - pH ca km 25oC.
62
Chng 5
n mn in ha hc
5.1.2 in cc phc tp - in cc hn hp
in cc phc tp l 1 h in ho gm cht dn in loi 1 tip xc vi cht dn in
loi 2, song trn b mt gii hn pha thng xy ra nhiu phn ng in cc v t nht c hai
h oxi ho kh xy ra v mt hnh thc.
V d: Kim loi ng nhng vo dung dch CuSO4 c mt H+ v oxi. Trn b mt gii
hn pha c th xy ra ng thi cc phn ng:
Ho tan kim loi ng:
Cu 2e Cu2+ (5.4)
ngha l c th tn ti h oxi ho kh:
Cu2+ + 2e U Cu (5.4a)
63
Hnh 5.1
in cc kim loi ng nhng dung dch ng sunfat
a) in cc n; b) in cc phc
Phn ng (5.6) xy ra sau mt thi gian t trng thi dng ng vi th dng hoc cn
gi l th hn hp hoc th n mn Em (xem hnh 51.b).
Hnh 5.2
S n mn in ho ca kim loi t trong dung dch cht in li
trng thi cn bng th tc phn ng thun vc bng tc phn ng nghch va. Trong
in ho s dng khi nim dng in hoc mt dng thay cho tc phn ng.
dq
I= = ZFv
dt
trong : I- cng dng in i qua bnh in phn (qua in cc);
dq - bin thin ca in lng;
66
Hnh 5.3
Gin quan h G* v th in cc E trn mt gii hn pha ca in cc. Kim loi - dung dch in li
67
ZFE
ia = ZFKa.CRed.exp (5.16)
RT
G o
trong : Ka = ka.exp
RT
Mt cch tng t:
ZFE
ic = ZFKc.COx.exp (5.17)
RT
G o
trong : Kc = kc.exp
RT
T cc phng trnh (5.16), (5.17) cho thy tc phn ng in ho ngoi s ph thuc
vo nng cht phn ng cn ph thuc vo th in cc.
Nu phn ng (5.10) xy ra iu kin cn bng, ng vi th in cc l Ecb, th phng
trnh ng hc ca phn ng anot v catot c th hin nh sau:
68
ZFEcb
ia = ZFKa. CoRe d .exp (5.18)
RT
ZFEcb
v ic = ZFKc. COx
o
.exp (5.19)
RT
i oo = ZFK so (5.25)
o o1
Vy i o = i oo .COx .CRe d (5.26)
Trong ng hc in ho trao i electron th i lng dng io l mt thng s rt quan
trng v n c quan h cht ch vi tc phn ng oxi ho kh no xy ra trn b mt
kim loi nht nh.
i vi mt h oxi ho kh nht nh, khi xy ra trn cc b mt kim loi khc nhau s
ng vi cc gi tr dng trao i io khc nhau i vi h oxi ho kh nghin cu, ngha l
dng trao i io ca mt h oxi ho kh c ph thuc vo bn cht kim loi. V vy, c th
dng gi tr io l thc o kh nng xc tc ca vt liu c dng lm in cc.
Da vo phng trnh (5.26) c th tnh c h s chuyn theo cng thc sau:
lg i o lg i o
= v =1 (5.27)
lg Co
lg COx
o
CoRe d Re d COx
o
69
Cc phng trnh (5.16), (5.17) biu din tc ca cc phn ng ring bit anot l ia v
catot l ic. Song khi h in ho b phn cc c mt dng in i qua mt h, ngi ta c khi
nim dng chung l i hoc cn gi l dng tng cng v khi :
i = ia + i c (5.28)
Quy c dng catot ic c du m v khi :
i = ia ic
C d ZF COx ZF
i = i o Re o
exp o exp (5.31)
CRe d RT COx RT
Phng trnh (5.31) gi l phng trnh ng hc in ho nu ln mi quan h gia tc
phn ng i v qu th v cn gi l phng trnh Butler -Volmen.
Nu giai on khuch tn cht phn ng din ra nhanh ngha l CoRe d = CRed v COxo
=
COx th ng hc ca ton b qu trnh in ho c khng ch bi s trao i in tch. Khi
phng trnh ng hc trao i electron c dng sau:
ZF ZF
i = i o exp exp (5.32)
RT RT
Khi p dng phng trnh (5.31) i vi h oxi ho kh ca in cc Fe3+, Fe2+/Pt:
Fe3+ + 1e U Fe2+
ta c phng trnh ng hc sau:
C 2 + ZF CFe3 + ZF
i = i o Fe o
.exp o
.exp (5.33)
CFe2 + RT CFe3 + RT
trnh (5.32).
Trn hnh 5.4 trnh by dng ng phn cc vi phng trnh (5.32).
70
Hnh 5.4
ng phn cc - s ph thuc ca mt dng in i (A/cm2) vo qu th (v).
a
Vy khi >> 1 th quan h i v c dng hm m (ng ia trn hnh 5.4).
a
trong : A c = c ln i o v Bc = 2,303c .
Hnh 5.5
S ph thuc ca vo lgi
(a) on thng Tafel anot; (b) on thng Tafel catot
d
h in ho khng phn cc nu khi phn cc ti vng th gn th cn bng Ecb c rt nh,
di
ngha l c gi tr io ln v RP rt nh.
Hnh 5.6
S ph thuc ca (v) vo mt dng i (A/m2)
d d
ab - H phn cc l tng ; a2b2 - H khng phn cc 0
di di
Hnh 5.7
S phn b nng cht phn ng gn st b mt in cc
a) Chuyn cht phn ng i n b mt in cc;
b) Chuyn sn phm i t in cc vo dung dch
Khi giai on trao i electron din ra nhanh v nng CSi cn li rt nh, ngha l CSi
0 th dng i t n dng gii hn id v bng:
Coi
id = ZFDi (5.46)
Mt khc, nu trn b mt in cc c sn phm i t trng thi bo ho Cibh , trn in
cc cng c dng i v c xc nh theo cng thc:
Cibh Coi
i = ZFDi (5.47)
v khi Cibh >> Cio ta c dng gii hn id bng:
Cibh
i = ZFDi (5.48)
Khi kim loi b n mn trong mi trng cht in li cha oxi, ng hc ca qu trnh
ho tan kim loi c khng ch l s khuch tn oxi v tc n mn c tnh theo cng
thc (5.46). Phng trnh (5.48) p dng tnh tc ho tan anot kim loi trong mi trng
cht in li b khng ch bi qu trnh khuch tn sn phm phn ng t b mt in cc vo
dung dch.
phng trnh:
RT
ECu2 + = ECu
o
2+ + o
ln CCu 2+ (5.49)
Cu Cu 2F
Khi phn cc catot ln, trn in cc s kh ion Cu2+ din ra nhanh, nng CsCu2 + gim
ng k, CsCu2 + 0 v sinh ra s chnh lch nng C gia b mt in cc v th tch
dung dch. Th in cc Ei c tnh theo phng trnh:
RT
= ECu
o
+ ln CsCu2 + (5.50)
E
i ( Cu2 +
Cu ) 2+
Cu 2F
RT CsCu2 +
c = Ei ECu2 + = ln o
(5.51)
Cu2 +
Cu
Cu 2F CCu 2+
2F
hoc i = id 1 exp c (5.54)
RT
Hnh 5.8
S ph thuc ca mt dng i(A/m2) v phn cc catot (v)
RT
trong Rp = (5.58)
ZFid
i o exp c
ic = c (5.62)
i
1 o exp c
id c
Phng trnh (5.62) l phng trnh ng hc in ho b khng ch hn hp ca s trao
i electron v s khuch tn. Trong iu kin nu io/id rt nh, ngha l io rt nh so vi id th
phng trnh (5.62) c dng ca phng trnh Butter - Volme v khi ng hc qu trnh
in ho b khng ch do s trao i electron.
Sau khi chia 2 v ca phng trnh (5.62) cho id ta c:
io
exp c
ic
= d
i c (5.63)
id i
1 o exp c
id c
ic
Nu c c gi tr rt ln th 1 , ngha l ic = id v khi ng hc ca qu trnh c
id
khng ch bi s khuch tn.
+
+ iH
ZZZZ
2H + 2e YZZZ
c
X
Z H2 (5.65)
H+
ia
H2 O
X H2 + OH
ic
hoc ZZZZ
2H2O + 2e YZZZ
H2 O Z
(5.66)
ia
O2
X 4OH
ic
hoc ZZZZ
O2 + 4e + 2H2O YZZZ
O2 Z
(5.68)
ia
iFe
Fe2+ + 2e YZZZ
ZZc
XZ Fe (5.69)
iFe a
a + ia = i c + i c
iFe (5.72)
H Fe H
+ +
a >> i c ; i c >> i a
Phng trnh (5.71) xy ra vi iu kin c s phn cc v iFe th
Fe H H
a = ic
iFe = im = i (5.73)
H
ZF
im = iFe
a ( ) Eam
= iFe
o exp
RT
(
Eam Ecb
Fe
) (5.74)
v im = iH
a ( ) +
Eam
= iH
+ ZF
o exp
RT
H+
(Em Ea ) (5.75)
Hnh 5.9
ng phn cc i E ca cc h oxi ho kh i vi Fe nhng trong mi trng axit
1. H Fe2+ + 2e U Fe
2. H 2H+ + 2e U Fe
3. H hn hp
ZF ZF
a = i o exp
iFe Fe
RT
(
Ei Ecb = i o exp
Fe Fe
)
RT
Fe
(
( Ei Eam ) + Eam Ecb )
ZF ZF
hoc a = i o exp
iFe Fe
RT
Fe
(
Eam Ecb .exp
RT
)
( Ei Eam ) (5.76)
Kt hp vi (5.74) ta c:
80
ZF
a = im.exp
iFe (Ei Em) (5.77)
RT
Mt cch tng t, i vi qu trnh catot gii phng hiro ta c phng trnh:
+ ZF
a = im.exp
iH (Ei Em) (5.78)
RT
Nu gi i l dng chung ca qu trnh st b n mn trong mi trng axit vi th phn
H+
a + | i c |; t Ei Em = , ta c:
cc Ei v bng i = iFe
ZF ZF
i = im exp exp (5.79)
RT RT
Phng trnh (5.79) c dng tng t phng trnh Butter - Volme (5.32) v ng vi
ng cong phn cc s 3 trn hnh 5.9.
RT
Chp nhn = = 0,5 v khi c s phn cc rt nh | | << th phng trnh (5.79)
ZF
c dng:
ZF
i = im. (5.80)
RT
RT i
hoc: = . = Rp.i (5.81)
ZF i am
d RT
Vy Rp = = (5.82)
di =0 ZF.iam
RP c gi l in tr phn cc.
Vy quan h i - E khi c s phn cc nh l tuyn tnh (ng cong 3 trn hnh 5.9).
Da vo vic xc nh RP t thc nghim cho php tnh trc tip c dng n mn im.
RT
Khi c s phn cc ln >> , phng trnh (5.79) c dng sau y:
ZF
i vi s phn cc anot l i = ia:
ZF
ia = im.exp a (5.83)
RT
RT RT
a = .2,303lgia .2,303lgim (5.84)
ZF ZF
i vi s phn cc catot: i = ic
ZF
ic = im.exp c (5.85)
RT
81
RT RT
c = .2,303lgic .2,303lgim (5.86)
ZF ZF
E(v)NHE
+
1 H+ /H 2
0,00 2+ E cb
Fe-2e Fe
-0,20 3
E m
-0,40 -
2+
2 Fe /Fe
-0,60 - E cb
H+ i m
-0,80 - Fe io 2H++2e H2
io
-5 -2 0 2 lgi (A/cm2)
Hnh 5.10
ng phn cc (V) lgi (A/cm2)
Cc phng trnh (5.84) v (5.86) c dng phng trnh Tafel (5.36) v (5.38) i vi
qu trnh phn cc anot v catot. Trn hnh (5.10) trnh by cc ng cong quan h gia th
phn cc E(V) v logarit mt dng lgi (A/cm2) i vi h st b n mn trong mi trng
axit khng cha oxi. T cc ng phn cc cho php xc nh c dng n mn im ca st
v th n mn Em.
Gia mt dng n mn im (A/cm2) tnh c t hnh (5.9) v s tn hao trng lng
ca kim loi sau khi n mn m quan h vi nhau theo phng trnh sau:
A.iam .t
m = (5.87)
ZF
trong : A- nguyn t lng ca kim loi tnh theo gam;
Z- ho tr ion kim loi;
F- s Faraday (96493 C);
im - ampe;
t- thi gian tnh theo giy.
82
m
T (5.87) tnh c tc n mn (g/S.t) = , trong S l din tch mu (cm2,
S.t
dm2, m2) v t l thi gian din ra qu trnh n mn (gi, ngy m, thng, nm).
E(V)
1 2
+
2H /H2
0,00 a b Ecb
Fe
-0,20 Em
1'
2'
-0,40
3
P
-0,60 Fe
Ecb
P' Zn
3' E m
4
-0,80
Zn
Ecb
-1,00 4'
lgi (A/cm2)
Fe Zn Zn
lgio -5 lgio -2 lgimFe
0 Zn
lgi m p' lgi m p
Hnh 5.11
ng phn cc E(V) - lgi(A/cm2)
( lg i )
2+ 2+
Zn
am > lg iam
Fe
l v th EZn
cb
/ Zn
< EFe
cb
/ Fe
v i Zn
o > io
Fe
P
Trong thc t i Zn
o.H2 < i o.H2 v th dng n mn ca km b gim i, ngha l:
Fe
( lg i )
Zn
am
P'
(
< lg i am
Zn
) P
2
84
3+
/ Fe2+
v: ZFe3+ + Ze ZFe2+ EFe
tn = 0,77 V
3+ 2+
Do th ca h EFe
tn
/ Fe
dng so vi h hiro cho nn kh nng nhn in t ca ion Fe3+
ln hn so vi ion H+ v thc y phn ng anot v lm tng tc n mn. C th ni rng
dng kh catot gm hai phn - kh ion Fe3+ v kh H+, vy:
i c H+ H + i c Fe3 + Fe2 + > i c H+ H
( 2 ) ( ) ( 2 )
C th ni rng, cc yu t nh hng n qu trnh kh catot, c bit i vi qu trnh
kh hiro rt c ngha i vi vic nghin cu n mn kim loi. V vy, vic nghin cu cc
c ch ca phn ng kh hiro c rt nhiu tc gi trn th gii quan tm trong lnh vc
in ho ni chung cng nh trong qu trnh n mn kim loi. Chi tit v vn s c
cp trong ti liu chuyn v ng hc cc qu trnh in cc.
Hnh 5.12
a) ng phn cc catot v anot ca h n mn in ho; b) gin Evans
MeZ + Ox
Trn hnh 5.12a cho thy Ecb Me < Ecb Re d do s chnh lch th nn hnh thnh pin n
mn, khi kim loi b ho tan Me Ze Me2+ chim u th, ng vi s phn cc anot (th
dch chuyn v pha dng) t O1 n A1. Ti vng kim loi c th dng xy ra phn ng
catot chim u th Ox + 2e Red v th dch chuyn v pha m t O2 n C.
MeZ + Ox
im O - th n mn Em nm gia Ecb Me
v Ecb Re d ng vi gi tr dng n mn im=|ic|
=|ia|.
85
v ia = ic = im.
Khi pin n mn c tnh n s phn cc catot v anot th dng im c tnh theo cng
thc:
Eci Eai
im = (5.94)
R
86
Eccb Eacb
Ta c: im = (5.96)
R + RPc + R Pa
Rin Rex
1 2
Rp Rp
a c
c c
Ecb
a E ia Ei Ecb
Hnh 5.13
S mch tng ng ca mt pin n mn gm hai in cc oxi ho kh n, trong :
Hnh 5.14
Gin Evans xc nh dng n mn im
Theo cng thc (5.97), nu E = Eccb Eacb cng ln th dng n mn ia cng ln.
Nu in tr R = Rin + Rex v cng ln th dng im 0.
Ngc li, khi R = 0 th E = 0, pin n mn b on mch vi gi tr imax. Trong thc t
iu ny khng xy ra v mi trng n mn (cht in li) in tr cht in li khng bao gi
t gi tr zero.
Khi pin n mn c in tr ni Rin cng ln th dng n mn t gi tr cng nh v lun
lun nh hn imax. on ab trn hnh 5.14 tng trng xt th iR do in tr Rin (b qua
Rex). Mt khc, khi in tr phn cc RPc v RPa cng ln th dng n mn im b gim cng
nhiu (xem hnh 5.15).
Vy da vo gin Evans cho php phn loi c cc trng hp khng ch dng n
mn ca pin n mn.
1) S hot ng ca pin n mn b km hm bi qu trnh anot, trong trng hp ny s
phn cc anot Ea rt ln so vi phn cc catot Ec, ngha l Ea > Ec ; khi th n mn
Em b dch chuyn ch yu v pha dng v gn st th cn bng catot Eccb (xem hnh
5.15a).
88
a) b)
Hnh 5.15
Gin Evans E(V) i(A/cm2)
1
v phn ng chung: Cu + O2 + H2O Cu2+ +2OH
2
i vi h st trong mi trng n mn gn trung tnh c mt oxi xy ra hai phn ng
(5.101) v (5.102). Nu mt dng trao i io ca phn ng (5.102) c gi tr nh, ngha l
giai on chuyn in tch xy ra chm th giai on ny khng ch ng hc kh oxi.
Tc kh oxi theo phng trnh (5.102) iC(O2 ) bng:
CSO2 4 c
iC(O2 ) = i O
o
o
exp O (5.104)
2
CO
2
RT
2
RT
Khi c s phn cc catot ln c th nng oxi trn b mt rt nh CSO2 0 v
ZF
sinh ra s phn cc nng , dng iC(O2 ) c tnh theo phng trnh Fick I v bng:
o
CO CSO2
iC(O2 ) = 4FDO2 2
(5.105)
trong DO2 l h s khuch tn ca oxi, l chiu dy lp khuch tn.
CSO2 iC(O2 )
hoc: o
=1 (5.108)
CO id
2
Kt hp (5.108) v (5.104) ta c:
iC(O2 ) O Fc
iC(O2 ) = i o (1 )exp 4 2 (5.109)
id RT
Sau khi bin i (5.109) ta c:
91
O Fc
o
iO exp 4 2
2
RT
iC(O2 ) = (5.110)
O Fc
o
iO
1 2 exp 4 2
id RT
RT
Ngc li, khi c phn cc ln c >> th s hng A rt ln so vi 1, t (5.111) ta
ZF
c:
iC(O2 ) = id (5.113)
Hnh 5.16
a) ng phn cc E(V) - lgi (A/cm2) ca h kim loi b n mn trong mi trng cht in li c mt oxi:
M ze Mz+ (5.116)
ng hc ca s ho tan anot ny tun theo phng trnh Butler - Volme, mt dng
anot tng theo s dch chuyn th v pha dng.
Kim loi th ng cng b ho tan thnh ion kim loi v chng b di chuyn qua mng th
ng n mt gii hn tip xc vi dung dch cht in li, sau i vo dung dch v tn ti
dng hirat.
Cn lu rng s ho tan mt kim loi trong vng hot ng v vng th ng c th to
ra cc ion c s oxi ho khc nhau (bng 5.1).
Bng 5.1. Dng ion cc kim loi ho tan hot ng v th ng
Fe Fe2+ Fe3+
Ni Ni2+ Ni3+
Cr Cr2+ Cr3+
V d: Khi phn cc anot kim loi thp Fe-17Cr trong dung dch H2SO4 0,5M thu c
ng phn cc anot gm cc min ho tan hot ng v th ng (xem hnh 5.17)
94
Hnh 5.17
ng phn cc anot thp Fe-17Cr trong H2SO4 0,5M
Trn hnh (5.17) cho thy vng AB - ho tan hot ng, vng CD - min th ng v DH
- min qu th ng.
d dng gii thch ng phn cc anot c th ng ca kim loi trong mi trng
axit, ta dng th m phng c trnh by trn hnh (5.18).
Hnh 5.18
ng phn cc anot kim loi trong mi trng cht in li c hnh thnh vng th ng
Bng s phn cc dng ngoi, AB ng vi vng ho tan hot ng, ion kim loi t kim
loi i vo dung dch, ng hc ho tan kim loi tun theo quy lut ng hc in ho trao i
in tch theo phng trnh Butler-Volme.
Ti im B t dng cc i ca s ho tan cn gi l dng ti hn iCr, ti lng sn
phm n mn ln c lu li trn b mt in cc bt u chuyn kim loi vo trng thi th
ng. Nu s gim dng t ngt rt ln khi dch chuyn th v pha dng th ng BC gn
nh thng gc vi ng CD, khi th ti im B gi l th bt u th ng. Trong thc t
n thng ln hn 90o, khi xut hin vng chuyn tip BC v dc ca ng
gc BCD
BC nh hn dc ng BC, ti C ng vi th EP gi l th th ng v c dng th ng
tng ng l iP. Dng iP ny rt nh.
Ti im D ng vi th ETP gi l th qu th ng, ti kt thc trng thi th ng v
bt u c s ho tan qu th ng nu dch chuyn th v pha dng ln hn th ETP. on
thng DH ng vi s ho tan qu th ng, s ho tan ny thng khng ng u v xut
hin dng n mn l v khi th qu th ng cn c gi l th nh thng mng. Ty
theo iu kin c th m th ETP c th dng hoc m hn th gii phng oxi.
Vy mt kim loi hoc mt hp kim c tnh th ng cao ngha l mng bo v cht xt
c in tr ln hn trong mi trng kho st, khi ng phn cc anot ca h tho
mn mt s yu t sau:
Gi tr dng iCr v iP rt nh, khng xut hin min ho tan hot ng.
Vng th ng CD cng rng cng tt, ngha l EP dch v pha m v ETP dch v pha
cng dng cng tt.
Sau y nu v d v ng th ng ca kim loi st trong dung dch H2SO4 0,5M (xem
hnh 5.19).
Hnh 5.19
ng phn cc anot ca st trong dung dch H2SO4 0,5M xut hin min th ng
Ngoi phng php p dng ngoi phn cc anot a kim loi vo trng thi th ng,
s th ng ho kim loi cn xy ra khi nhng kim loi vo dung dch nc cha cht oxi ho
m th cn bng ca h oxi ho ny ERedox dng hn th th ng EP (xem hnh 5.20).
97
Hnh 5.20
ng phn cc ca h n mn kim loi ti th ng
Trn hnh (5.21) cho thy th cn bng ca oxi ERedox = o2 = +1,23 V (NHE) rt dng
so vi EP. V th d dng a kim loi vo trng thi th ng v p ng cc iu kin
(5.121) v (5.122).
Hnh 5.21
S ph thuc ca lni vo E(V) i vi h kim loi b n mn t to ra th ng trong mi trng c mt
oxi vi o > EP
2
lgi(A/m2)
ico2 (PO2,1)
lgi1m P
B
ico2 (PO2,2)
lgi2m
Y1 N
D
C
lgi1'm
A X1 X E(V)
2 1
Ep EO2 EO2
Hnh 5.22
ng phn cc lni - E(V) ca h n mn kim loi pin thng kh oxi c hnh thnh mng th ng
5.7.3 Hp kim v s th ng ho
Khc vi kim loi nguyn cht, cc hp kim c bn c hc cao, song hp kim cng c
kh nng chng n mn cao c th hin bng kh nng th ng cao ca chng.
Nh bit trong cng mt mi trng, kim loi no c dng ti hn iCr cng nh v th
bt u th ng cng m th cng d dng b th ng.
V d trong mi trng axit H2SO4 1N, kim loi crom d dng i vo trng thi th ng
hn l st (xem hnh 5.23) v iCr
Fe
> iCr
Cr
v Cr
p < p .
Fe
Hnh 5.23
ng phn cc anot c min th ng trong H2SO4 1N
1 - Kim loi crom; 2 - Kim loi st
Hnh 5.24
ng phn cc anot ca hp kim Fe13CrxMo trong dung dch HCl 1M
5.7.4 Thuyt th ng ho
Ngy nay tn ti hai l thuyt gii thch hin tng th ng ho:
Thuyt to mng: Theo l thuyt ny s th ng ho ca kim loi trong mi trng cht
in li l do s to mng (hnh thnh pha mi trn b mt gii hn pha kim loi v dung dch
cht in li) trn b mt kim loi tip xc vi mi trng n mn. dy ca mng th ng
c mt vi nanomet n c vi chc nanomet. C tc gi cho rng chiu dy mng th ng
tng theo dch chuyn th v pha dng. V d mng th ng Cr trong dung dch H2SO4
tng t 0,5 n 4,5 nm khi tng th.
Thuyt hp ph: Cc tc gi A.N. Frumkin, Ia.M. Koloturkin cho rng s th ng
kim loi trong mi trng n mn l do s hp ph ca oxi trn b mt kim loi. V d oxi
hp ph trn platin mt lng rt nh, platin b th ng v bn vng chng n mn vi
mi trng xm thc. S hp ph oxi trn cc tm hot ng c trn b mt kim loi (c khi
ch cn 1% din tch) lm cho kim loi b th ng.
104
Chng 6
Cc dng n mn
1.11 n mn u
Dng n mn ny rt ph bin (xem hnh 6.1) vi nhng c im sau: tc n mn
mi ch trn b mt gn bng nhau. V d thp t trong mi trng H2SO4. nh gi tc
n mn ny ngi ta thng s dng phng php trng lng (g/cm2.gi) hoc da vo
gim chiu dy ca mu th nghim Pmm/ nm hoc mA/cm2.
Hnh 6.1
Dng n mn u
1.12 n mn cc b
Dng n mn ny xy ra u tin ti mt s phn din tch b mt kim loi tip xc vi
mi trng n mn. Hin tng n mn cc b ny cng rt ph bin v rt a dng, c th
chia thnh cc loi sau:
Thp Al
Kim loi Ni Cu Zn Mg
cacbon 99%
105
Em(NHE) 0,046 0,01 0,335
0,667 0,809 1,355
Mt s trng hp xy ra n mn ganvanic:
+ Cc inh c vt hoc cc tm thp m km trong mi trng cht in li, km c in
th m hn kim loi nn v s d dng b n mn theo c ch ganvanic.
+ Cc c vt bng thp s b n mn khi tip xc vi cc vt liu ng thau trong mi
trng nc bin.
Trn c s ng cong phn cc c th gii thch hin tng n mn tip xc cho mt
s trng hp sau y:
V d 1: H tip xc ca Fe v Zn trong mi trng axit H2SO4 long khng c oxi.
Hnh 6.2
Cc ng phn cc ca h n mn tip xc Fe-Zn trong mi trng axit H2SO4 long khng c oxi
th n mn Em
Zn
.
106
Tng t i vi pin (6.2), ti vng anot st b ha tan v cng gii phng hiro trn
H2
vng anot, vy ti EFe
m ta c i m = i a = i c,Fe .
Fe Fe
Khi so snh s hot ng ca hai pin (6.1) v (6.2) cho thy dng n mn ca Zn im
Zn
ln
hn dng n mn ca st im , iu ny l do trong mi trng axit km hot ng hn st.
Fe
Nu ta gi thit dng iH
o,Zn = i o,Fe th dng n mn ca km cn ln hn so vi st rt
2 Fe
nhiu.
+ Nu st v km tip xc vi nhau ta xem h cn li mt pin, khi vng catot trn c hai
Zn +Fe
vt liu u thot kh hiro. Vy Em ti ch tip xc ca hai kim loi c k hiu l Em
Zn + Fe
ng vi dng n mn im v tng dng n mn ca hai kim loi km v st hoc bng tng
dng n mn iH
c
2
trn hai kim loi (xem hnh 6.2). Gi tr ny ln hn dng n mn im
Zn
hoc
im .
Fe
Zn + Fe H2 H2
im = im
Zn
+ iFe
m = i c,Zn + i c,Fe (6.3)
V d 2: H tip xc ca Fe v Ni trong mi trng H2SO4 long khng c oxi v gi thit
rng tc phn ng gii phng hiro trn hai kim loi bng nhau.
Trn hnh 6.3 cho thy trong mi trng H2SO4 long tc n mn Ni nh hn tc
n mn ca Fe. Trn hnh cng cho thy: Khi kim loi Ni tip xc vi Fe th th n mn
+ Fe
ENi
m nm gia 2 gi tr th n mn ring bit ca st v niken, ngha l:
Ni + Fe
m < Em
EFe < ENi
m
+ Fe
v iNi
m = iH 2 H2
c,Fe + i c,Ni = i m + i m
Ni Fe
+ Fe
v iNi
m > iFe
m > i m
Ni
Hnh 6.3
Cc ng phn cc ca h n mn tip xc Ni+Fe trong dung dch H2SO4 long khng c oxi
107
Zn + Pt
v im > im
Zn
Hnh 6.4
ng phn cc ca h n mn tip xc Zn-Pt trong mi trng axit H2SO4 long khng c oxi
Hnh 6.5a
ng phn cc ca h n mn tip xc Zn-Pt trong mi trng axit (din tch Pt tng ln)
V d kim loi st (Fe) t trong dung dch NaCl, song c s chnh lch nng kh O2
ho tan ti hai vng trn b mt kim loi. Ti nng oxi ca khng kh ho tan vo nc
vng gn mt nc cao hn trong th tch.
Vy mi vng l mt pin n mn m s ho tan kim loi gn lin vi s kh oxi.
Mch pin ca h ny c th m phng nh sau:
Fe (O2)2 / NaCl / FeFe / NaCl / (O2)1 Fe (6.5)
Trong p sut kh O2 (khng kh) P( O2 )2 > P( O2 )1 . S ch to c hnh dung theo
hnh v 6.5b.
5
3 5 1. in cc st;
5. ng dn kh
Hnh 6.5b
S ch to pin n mn kim loi khng kh
Khi hai in cc 1 v 2 khng ni vo nhau (tip xc 2 ngt mch) ta c hai pin n mn,
mi pin gm cc in cc l st v in cc oxi. Hai in cc oxi c nng khc nhau. Cc
pin hot ng, dng n mn im v th n mn ca chng c xc nh da vo ng phn
cc (xem hnh 6.6).
110
Hnh 6.6
ng phn cc ca h n mn st trong dd NaCl c thng kh
id2 .
O2) ng vi im ct ca 2 ng 1 v CC1.
Vy hai kim loi st t trong hai cc (hnh 6.5b) c kch thc hnh hc v dung dch
NaCl hon ton ging nhau, nhng tc n mn ngn c nng oxi ln c dng n mn
ln.
PO22 > PO1 2 ng vi iFe
m2 > i m1
Fe
111
K
T- Pha rn thp ;
K- Pha kh - khng kh ;
N- Pha lng - dung dch
2 nc bin ;
T
1- Vng b n mn ;
N 2- Lp g
1
Hnh 6.7
n mn mn nc
Hnh 6.8
n mn lng ng
1. Kim loi; 2-2. Vng giu oxi; 3. Vng ngho oxi do che khut; 4. Vt lng ng
Hnh 6.9
ng phn cc vng ng vi s c mt n mn im
1. ng phn cc anot (vng) trong dung dch khng c ion halogen;
2. ng phn cc anot (vng) trong dung dch c cha ion halogen
Hnh 6.10
Dng n mn l ca thp th ng trong mi trng c mt Cl
6.5.1 n mn nt do ng sut
n mn nt l do s nt gy bi ng sut ko v mi trng n mn gy ra.
Hu ht cc hp kim kt cu dng trong k thut (v d cc kt cu thp ca cu, gin
khoan, tu thuyn ...) u c th b rn nt v sau b gy di tc dng ca mi trng n
mn ng thi di tc dng ca lc ko. Trong qu trnh cc cu kin b n mn dng nt
di ng sut phn ln b mt kim loi khng b xm hi r rng, nhng li c nhng vt nt
nh xuyn qua chng, v th hin tng n mn nt rt nguy him, c bit xy ra trong cc
bnh nn kh.
C th ni rng loi n mn ny rt phc tp, cho n nay ngi ta vn cha bit y
v n.
Di y l mt s yu t nh hng n hin tng n mn ny:
a) Mt s mi trng c th gy ra s n mn nt do ng sut i vi mt s vt liu
Thp khng g FeNi8Cr18 trong dung dch c cha ion Cl (BaCl2, NaCl-H2O2...);
Thp thng trong mi trng cha OH hoc NO3;
Hp kim nhm trong dung dch cha ion Cl, trong nc bin, hi nc;
Hp kim ng trong mi trng kh NH3 hoc trong dung dch cha ion NH4+, tip xc
vi cc hp cht amin, hi nc
Hp kim magie trong dung dch NaCl-K2CrO4;
Hp kim titan trong HNO3 bc khi, nc bin
b) Cc giai on ca n mn nt
Khi u ca s n mn nt
S n mn nt do ng lc bao gm nhiu giai on: Pht sinh vt nt (t vi giy n
nhiu ngy), s lan truyn vt nt (tc nt 1011 102 m/ngy), cui cng l giai on gy
v ti trng c hc qu cao. Di tc dng ca ng sut ko trn b mt nhn ca kim loi
thng xut hin cc ch hng cc b gi l bc trt, ti xy ra s khi u n mn.
Nu kim loi nhanh chng b th ng th khng nguy him, cn nu thi gian th
ng ko di th s c s n mn im v nh vy l khi u s n mn nt. C trng hp
s khi u n mn nt khng phi l bt u t n mn im m xut hin vt nt ti cc
bin gii ht tinh th. Nu bin gii ht khng ng nht v thnh phn ho hc cng gy ra
s n mn, khng nht thit l dng vt nt.
Pht trin n mn vt nt
S lan truyn cc vt n mn nt c gii thch bng nhiu gi thuyt:
S lan truyn cc vt nt xy ra ch yu theo bin gii ht v hot ng tng t n
mn ranh gii. Ti c s phn cc anot, kim loi b ho tan.
S lan truyn cc vt nt do bin dng ca mng bo v b nt gy, tc gy mng
hoc cn gi l tc bin dng, tc lan truyn khi c ti trng tnh ph thuc vo cc yu
t:
+ Kh nng tip xc ti u mt ca vt nt vi cc phn t xm thc, v d ion Cl hoc
oxi.
117
V d ho tan km trong hp kim ng thau bng dung dch axit H2SO4 long. Sau mt
thi gian ngm mu, km b ho tan v cn li mt khi ng xp. S n mn nh vy gi l
s n mn chn lc. Dng n mn ny xy ra trong nhng iu kin nht nh - hp kim l
dung dch rn ng th, gi tr th ca kim loi b ho tan m hn so vi kim loi bn trong
mi trng n mn.
i vi hp kim Cu-Zn ngi ta gi thit rng cc ion km chuyn n b mt b n mn
bng dng khuch tn t th tch
Mt khc c th gi thit cho rng c hai kim loi Cu v Zn u b ho tan do phn ng
anot, sau ng b kh v kt ta tr li.
S n mn chn lc hp kim ng niken (Cu-Ni) hoc hp kim thp khng g FeNi8Cr18.
trnh hin tng n mn chn lc nn s dng cc hp kim cha t kim loi c in
th m. V d gim hm lng km trong hp kim ng km. Thng vi lng km trong
hp kim nh hn 15% th km khng b ho tan. Nu thm vo hp kim 1% Sn hoc mt
hm lng nh asen (As) th tc n mn chn lc ng thau gim mt cch ng k.
6.5.1 n mn mi mn
Khi kim loi b vt th rn tc ng ln b mt kim loi lm cho cc ht bi kim loi tch
ra khi b mt ca s mi mn. Mi mn c th gy ra do dng chy ca cht lng tc ng
ln b mt vt rn.
Khi s mi mn lm mt mng th ng, trong mi trng xm thc, kim loi d dng b
n mn. C th ni rng n mn mi mn rt a dng.
6.5.1 n mn do ma st
n mn do ma st thng gp ti ch ghp ni ca vng bi trn mt trc.
trnh loi n mn ma st ngi ta hn ch s chuyn ng lp li nhiu ln, ti ch
ghp cht cn c lp m bng kim loi mm, v d ng hoc nhm mt pha hoc c hai
pha hoc photphat ho sau tm du, ph lp mng cht hu c polytetrafloruaetylen
(teflon), lp mng MoS2.
Nu ma st do dng chy gy ra th phi hn ch dng chy ri lon hoc cho thm c
ch vo hn ch s mi mn dng th ng.
trong : H - m tng i;
P - p sut ring phn ca hi nc trong kh quyn ti nhit kho st;
Po - p sut bo ho ca hi nc ti nhit kho st.
n mn kh quyn t - qu trnh n mn kim loi xy ra khi m tng i gn
100%, c git nc ngng t trn b mt kim loi, hoc c git ma, to ra lp cht in li
trn b mt kim loi. Hin tng n mn kim loi ny xy ra theo c ch in ha.
Hnh 6.11
Tn tht trng lng (g/m2) ca thp cacbon theo thi gian (ngy)
120
trong : P l tc n mn;
a, b l cc h s;
t l thi gian nm.
6.5.3 n mn trong kh quyn bin
Trong kh quyn bin lun lun c ion Cl, v th tc n mn kim loi tng ng k so
vi min nng thn.
121
Hnh 6.12
S n mn ct thp btng
Ti anot: Fe 2e Fe2+
1
Tai catot: O2 + 2e + H2O 2OH
2
Qu trnh n mn ch xy ra khi vng catot c H2O v O2. Nu in tr ca btng rt ln
th tc n mn nh (5 7.104 /cm).
Oxi l cht ng vai tr kh catot thc y s ho tan kim loi, song Cl ng vai tr rt
quan trng.
Khi c mt Cl, in tr btng b gim d lm cho dng n mn tng ln v n ng vai
tr khi mo cho phn ng thng qua phn ng ph v mng th ng vi s hnh thnh hp
cht phc:
Fe + 3Cl FeCl3 + 2e
FeCl3 + 2OH Fe(OH)2 + 3Cl
Phn ng catot to ra OH, pH tng ln cho nn s n mn su trong l b gim, s n
mn tip tc th nng Cl trong l phi ln thay th OH, nu thiu Cl s sinh ra ti
th ng. Vi nng Cl = 0,5% so vi khi lng ximng th xy ra s lan truyn khi
mo n mn. Mt khc, vi s c mt Cl, xy ra s n mn l lm cho t l in tch
catot/anot ln, mt dng s tng cao.
nng cao cht lng cng trnh btng ct thp c th s dng cc bin php sau:
+ To mt lp v btng bm chc ct thp, cht xt, ph kn hn ch s thm nc v
thm cc cht gy n mn ca mi trng.
+ Bo v bng phng php in ha - bo v catot.
+ Sn ph lp v btng bng cc loi sn v c hoc hu c.
6.5.6 n mn vi sinh
124
SO24
Vi khun 2
S + 4O
S c mt sn phm S2 v oxi thc y qu trnh n mn in ho, ngha l oxi sinh ra s
phn ng vi nguyn t H mi sinh ca phn ng catot. Mt khc, s c mt S2 s phn ng
vi Fe2+ to ra sulfua st:
Fe2+ + S2 FeS
C hai yu t trn s thc y qu trnh n mn in ho st. Sn phm n mn thng
dng mu en, mu ca sulfua st, c dng xp cng gp phn lm d dng kh oxi.
125
Chng 7
Nghin cu cc bin php chng n mn kim loi nhm mc ch nng cao tui th cc
cu kin, cc cng trnh c ngha khoa hc v c bit em li hiu qu kinh t ng k.
Cn c vo c ch n mn in ho cng nh iu kin hot ng ca cc pin n mn c
th a ra cc bin php sau y nhm mc ch gim tc n mn kim loi n mc thp
nht. cng chnh l mc tiu hng ti ca cc phng php bo v.
7.1 La chn vt liu kim loi thch hp
Trong phn ny s ln lt gii thiu mt s kim loi, hp kim thng dng v hai phng
din: tnh cht n mn ca vt liu v bin php nng cao bn chng n mn ca n.
7.1.2 Gang
Hm lng cacbon trong gang ln hn 2%.
Gang xm cha 2 4% C v 1 3% Si. bn chng n mn ca n trong nc cao
hn thp mm, nu thm 3% Ni bn c hc tng ln, bn chng n mn c ci thin.
Trong gang trng lng cacbon tn ti dng Fe3C, n cng v gin, khi b n mn Fe3C
ri vo dung dch li cc l cha graphit v thng gi l n mn graphit ha.
Nu hm lng Si trong gang ln hn 14% loi ny c tn thng mi l Duriron th
vt liu ny c chng n mn rt cao, thng c dng ch to cc thn bm.
Gang Niben c thnh phn Ni (14 32%), Cr (1,75 5,5%), Cu (<7%) c bn c hc
v bn chng n mn rt cao trong mi trng H2SO4.
Thp ny c dng trong cng nghip ho cht, thc phm v cng nghip t.
Bng 7.1. K hiu cc loi thp khng g thng dng
Th % nguyn
Loi %Cmax %Cr %Ni
t t khc
3,5
1 210 0,15 16 18 5 7 Mn
5,5
1 Si
2 304 0,08 18 20 8 12
(Max)
1 Si
3 304L 0,03 18 20 8 12
(Max)
10
4 316 0,10 16 18 2 3 Mo
14
10
5 316L 0,03 16 18 2 3 Mo
14
0,07 Ti,
6 322 0,07 17 7
0,2 Al
11,5
7 410 0,15 -
13,5
0,5
8 430 0,12 14 18 -
(Max)
1,25
9 431 0,2 15 17 -
2,5
7.1.4 ng v hp kim ng
ng v hp kim ng l loi vt liu dn nhit v dn in tt, c bn c hc v bn
chng n mn cao. Gi tr in th ca ng thay i theo mi trng:
Gi tr in th
0,34 0,06 0,15
E(V)
Trong mi trng axit khng cha oxi, ng khng b n mn gii phng hiro. S n
mn ng ch xy ra trong mi trng c cha oxi hay l cha cc cp oxi ha kh c in
th EoRe d > ECu2
o
+ = 0,34 V . Nu c mt cc ion hoc hp cht Cl , NH3, CN , khi th
Cu
cn bng ca ng ECu
o
2+ chuyn v pha m hn, cho nn n b n mn to thnh cc hp
Cu
cht phc.
V d: Cu trong dung dch Cl 25oC xy ra phn ng:
Cu + 2Cl CuCl2 + 1e
CuCl2 + 1e U Cu + 2Cl
hoc
aCuCl
v th in cc: cb
ECuCl = 1,94 + 0,059 lg 2
2
2
Cu aCl
6
vi aCl = 1 v aCuCl = cCuCl = 10 M
2 2
th cb
ECuCl = 0,160 V
2
Cu
130
Titan khng bn trong H2SO4 v HCl tinh khit, nhng li bn trong axit c cha cc ion
Fe3+ (FeCl3) hoc Cu2+ (CuCl2).
Hp kim Ti c Mo 30% bn trong dung dch HClO, trong Ti c mt lng nh Pt, Pd
hoc cc kim loi qu khc th bn chng n mn ca Ti tng ln.
Khi s dng Ti cn phi lu mt s trng hp sau:
Khi kim loi Ti hp ph H2, n tr nn gin (v d Fe tip xc vi Ti trong
mi trng axit).
Khng s dng Ti trong cc dung dch tng i tinh khit: HCl, H2SO4, HF
hoc kh Cl2 kh.
Khi tip xc vi cht do c cha Pb vi Ti th Ti b ph hu.
K hiu hp kim
Th Thnh
H hp kim
t Tiu chun VN Tiu phn %
(TCVN) chun AA
(*)
Loi cng
2 Al 99,0 1100 99,0 Al
nghip
4,4Cu-
3 Al-Cu-Mg AlCu4,4Mg1,5Mn0,6 2024
1,5Mg-0,6Mn
1,2Mn-
4 Al-Mn AlMn1,2 3004
0,12Cu
0,3Cu
4,5Zn-
1,4Mg-0,12Cr
6 Al-Zn-Mg AlZn4,5Mg1,4 7005
-0,4Mn-
1,5Zr
a) Phng php ha hc
Cc phn ng kh loi oxi:
O2 + 2Na2SO3 2Na2SO4
Phn ng ny xy ra rt chm, c th tng tc bng xc tc CO2+ (103 ppm). Nu d
sulfit s gy n mn
hoc: N2H4 + O2 2H2O + N2
nhit cao hirazin b phn hu:
3N2H4 N2 + 4NH3
S c mt ca NH3 c th gy ra s n mn cc chi tit bng ng v cc hp kim ca n.
Mt khc c th dng cc hp cht amin RNH2 loi tr ion H+:
RNH2 + HOH RNH3+ + OH
OH + H+ HOH
Kh kh CO2 chng li s gim pH ca mi trng.
b) Cc phng php vt l
un nng dung dch ui oxi.
X l bng chn khng lm gim nng oxi.
lgi (A/cm 2 )
ic
lgi c(Redox)
lgi Cr 1
lgi m
E(V)
ECr EP ERedox +
Hnh 7.1
ng phn cc anot xut hin th ng
1. Cht c ch c nng gy th ng;
2. Cht c ch c nng cha gy th ng
Lp oxit ny ngn cch b mt kim loi vi mi trng n mn. Song nu trong dung
dch c mt cc cht kh Cl hoc H2S s lm gim qu trnh to mng oxit v kh nng th
ng s b gim, tc n mn kim loi tng ln.
Nu nng cht c ch b gim v lp oxit khng c tc dng bo v th kim loi d b
n mn dng l (ng 2 hnh 7.1).
i vi mt s cht c ch th ng CrO24 , NO2 th nng ti hn nm trong khong
103 104mol/l. Tron nc ca cc h thng lm mt khi nng ion Cl tng, nhit tng
th nng cht c ch phi tng. H thng lm lnh tun hon bng nc ngt c pH = 8 cho
cc ng c iezen vi nng cht c ch Na2Cr2O4 bng 5.103 mol/l s khng b n mn.
Ngoi ra c mt s cht c tc dng nh l cht c ch th ng: NaOH, Na2CO3, cc
mui photphat, silicat, borat i vi thp trong mi trng gn trung tnh c mt oxi ho
tan.
Cc cht dng nitrit, benzoat, photphat, mercapto, benzotriazol thng c dng
trong cc h lm lnh ca ng c t.
Trong cc h thng lm mt, s kt ta ca cc mui CaCO3, MgCO3 ln cc thnh ng
dn nc cng c tc dng ngn cn qu trnh n mn kim loi, song trong mt gii hn no
li khng c li cho s truyn nhit.
136
b) Cht c ch hp ph khng gy th ng
a s cc hp cht hu c c cha N v S u c tc dng c ch nng cao bn chng
n mn kim loi trong mi trng n mn.
Cu trc phn t ca cc cht c ch hu c thng gm hai phn:
Mu khng phn cc c kch thc ln do lin kt ca cc nguyn t C v H k nc.
Phn phn cc gm cc nhm chc: SH (mercapto), NH2 (amin), OH (hiroxyl),
COOH (cacboxyl) a nc.
Cc nhm phn cc ny nh ln b mt kim loi dng hp ph vt l (i khi l hp
ph ho hc) cn phn khng phn cc nm trn b mt che ph cc tm hot ng ca kim
loi. V vy c tc dng lm c ch qu trnh n mn kim loi. Cc cht c ch cng c hiu
qu nu kh nng hp ph ca chng ln b mt cng ln v cng bn cht.
S hp ph ca cc hp cht ny c th km hm qu trnh catot - gi l cht c ch catot
hoc c ch qu trnh anot - gi l cht c ch anot. C trng hp cht c ch km hm c
hai qu trnh catot v anot. S c ch cc qu trnh in ho ny u lm gim tc n mn
kim loi.
Cc cht c ch hp ph thng dng trong mi trng axit. u im ca loi c ch ny
l lng cht c ch nh song vic s dng cht c ch c th dn n s ph v bn c
hc ca vt liu. V d s hiro ho vt liu lm tng gin ca vt liu.
Sau y l mt s cht c ch s dng cho cc mi trng khc nhau:
Hp cht amoni nitrit iazopropyl c ch bay hi i vi cc kim loi mu - bo v Cr,
Sn, Monel.
Hp cht ixiclohexyl amoni nitrit - c ch bay hi bo v thp.
Hp cht CrO24 (300 500 ppm), canxipolyphotphat (15 37 ppm), silicat (20 40 ppm),
c ch chng n mn kim loi ca h thng nc lm lnh tun hon.
Hp cht nitrit, benzoat, photphat, natrimercaptobenzotiazol, benzotriazol c ch chng
n mn kim loi cho h thng lm lnh t.
Hp cht phenylthioure, thioure, mercaptan c ch chng n mn trong qu trnh ty
g.
7.3.2 Lp ph v c
7.3.2.1 Lp photphat ho
To lp mui photphat cc kim loi Mn, Fe hoc Zn ln trn nn thp ca cc loi chi tit
hoc cc kt cu - v t, tu ho Mng ny c tnh bo v chng n mn km v khng
dng n lm lp bo v, song n kt hp vi cc lp ph nh sn s to ra lp bo v c cht
lng cao.
Vic photphat ha chi tit tin hnh 96 98oC vi thnh phn g/l: Mono photphat km 35
37, nitrat km 52 53, H3PO4 t do 15 16.
Hoc c th tin hnh photphat ho nhanh vi thnh phn g/l: Oxit km 23 25, ortho
photphoric axit 27 29, HNO3 30 35, NaNO2 1 1,2, NaClO 0,3 0,5, pH = 2,4 2,7, to t
25 30oC.
S hnh thnh lp photphat ho xy ra theo cc phn ng sau:
Fe Fe2+ + 2e
140
v 2H+ + 2e H2
C cc phn ng thu phn:
nc nng
ZZZZZZZ
X
Mn(H2PO4)2 YZZZZZZZ MnHPO4 + H3PO4
nc nng
3MnHPO4 ZZZZZZZ
X
YZZZZZZZ Mn3(PO4)3 + H3PO4
Ion Fe2+ s tc dng vi H3PO4 to thnh cc mui photphat ca Mn v Fe th cho 2H+
hoc 3H+ ca axit H3PO4 to ra mui kt ta v to mng trn cc chi tit.
Vic to mng photphat ho ln cc cu kin bng st thp, sau ph sn ln s c
mt mng vng chc c chng n mn cao (chi tit c trnh by trn cc ti liu chuyn
kho).
Oxi ha nhm
Bng phng php phn cc anot nhm trong mi trng axit H2SO4, axit oxalic to
ln b mt nhm v hp kim nhm mt lp oxit bo v chng n mn kim loi.
V nguyn tc xy ra cc phn ng sau:
Trn anot:
Al Al3+ + 3e
v c ion O2 to ra do:
H2O 2H+ + O2
Cc ion Al3+ v O2 khuch tn ngc chiu nhau, tc dng vi nhau thnh Al2O3. Mng
Al2O3 pha tip xc vi cht in li b ho tan mt phn tr nn xp to iu kin cho cht
in li xm nhp vo pha trong. Vy trn anot c hai qu trnh:
+ St b mt kim loi nhm to ra lp oxit nhm cht st bm chc ln nn
nhm gi l barie trong.
+ Pha ngoi tip xc vi dung dch cht in li c mt phn b ho tan, to ra
lp mng xp pha ngoi (xem hnh 7.2).
3e
dd cht in li
3+
Al
O2-
+
HOH H
Ant Al3+
O2-
1 2
7.3.3 Lp ph hu c
Sn v vecni l nhng sn phm lng, c th qut hoc phun ln b mt vt liu kim loi
hoc phi kim loi trang tr, bo v chng n mn kim loi hoc cch in, dit nm mc...
Sn l mt h huyn ph gm cc ht mu (oxit kim loi hoc mui kim loi) phn tn
trong cht kt dnh hu c. Vy thnh phn sn gm:
a) Pha lng gm dung mi ho tan cht kt dnh, to ra trn b mt mt mng cht rn
lin tc sau khi dung mi bay hi (cht kt dnh c nhiu loi - nha ankyt, bitum, nha than
, nha vinyl, nha epoxi, nha polyurethan).
Cc ph gia: nhng cht vi mt lng nh cho vo ci thin mng kt dnh: cht lm
cho sn mau kh do s tng nhanh qu trnh oxi ha cht kt dnh. Nhng cht ny thng l
mui ca mt s kim loi Co, Pb, Mn, Zn, Zr
Cht hot ng b mt ci thin thm t ca sn v b mt kim loi.
Cht to nh tng lm cho sn dng nh n nh.
Cht phn tn c nhim v ui nc ra khi b mt sc t (pigment), lm
tng cng bm dnh ca mng sn ngay c khi b mt kim loi b m t.
Cht mu (pigment), mu hu c hoc l cc oxit kim loi, mui kim loi.
Cht chng lng.
Cht tr vi khun, hu h (Cu2O).
Sau y l mt s cht kt dnh v pigment thng dng:
+ Cht kt dnh:
142
7.3.4 Lp ph cht do
C nhiu loi nha bn trong cc mi trng n mn, v vy ngi ta ph trc tip cc
lp cht do ln kim loi.
V d dng nha PVC, nha teflon. Nha ny bn vi axit v kim, cc dung mi hu c
cho n 250oC. C th dng cc loi nha ny ph ln cc kt cu thp.
Hnh 7.3
ng phn cc ca h st b n mn trong mi trng axit long khng cha oxi
Ti im O, ng vi th n mn Em v c dng n mn:
H2
im = iFe
a = ic
Hnh 7.4
S bo v catot bng dng ngoi
1. Vt cn c bo v (ng ng dn du di t);
2. Cht n dn in;
3. in cc ph anot (ng thp, ng silic, graphit, titan);
4. Ngun in mt chiu;
5. in tr iu khin dng;
6. Mi trng t
Trong mi trng trung tnh c oxi, tc ho tan kim loi b khng ch bi s khuch
tn oxi vi im = idO = 101 A/cm2. y l phng php bo v c hiu qu kinh t cao.
2
Trong mi trng axit phng php ny khng kinh t v s tiu hao in nng rt ln.
Ngi ta p dng phng php ny bo v cc ng ng dn nhin liu, xng du
nm di t.
Hnh 7.5
S bo v chng n mn kim loi bng anot hy sinh
in th lm vic
Hp Mi Dung lng
(so vi in cc bc trong
kim trng Ah/kg
nc bin)
Al- Nc
1,0 1,05 2600 2850
Zn-Mg bin
Al-
-nt- 1,0 1,10 2300 2650
Zn-In
Al-
-nt- 1,0 1,05 925 2600
Zn-Sn
Zn-
-nt- 1,05 780
Al-Cd
146
Mg-
-nt- 1,50 1230
Al-Zn
Mg-
-nt- 1,7 1230
Mn
7.4.3 Bo v anot
Phn cc anot a kim loi vo trng thi th ng (bo v cc thng kim loi cha
axit) ch cn dng in nh, tiu hao t nng lng. i vi phng php ny cn c thit b
chnh xc, an ton trnh s hot ha dn n s ho tan ca vt c bo v.
147
Chng 8
8.1 M u
Nhm mc ch phn loi v nh gi nh hng ca mi trng n bn chng n
mn ca vt liu trong iu kin t nhin cng nh iu kin gia tc th vic la chn phng
php nh gi tc n mn c ngha rt quan trng.
C rt nhiu phng php nh gi tc n mn.
Ngi ta dng mt thng hoc dng knh hin vi quan st trng thi b mt kim loi b
n mn cho php nh gi nh tnh v phn loi n mn theo dng n mn u hoc dng n
mn cc b (n mn im, n mn khe).
Bng 8.1 Thang phn loi bn chng n mn vt liu kim loi
Siu bn 0,001 1
0,001 0,005 2
bn cao
0,005 0,01 3
0,01 0,05 4
C bn trung bnh
0,05 0,1 5
0,1 0,5 6
bn thp
0,5 1,0 7
1,0 5,0 8
bn rt thp
5,0 10,0 9
Cc phng php phn tch nng kim loi b ho tan vo mi trng n mn v suy
ra tc n mn kim loi.
S dng cc phng php in ho.
Sau y s trnh by mt s phng php c th.
3 E
5
1
Ea
2
1
4 2
thi gian (t)
8
6 5
7
4 A
2
1
3
Hnh 8.3
S thit b o ng phn cc (Galvanostatic)
1. in cc lm vic (WE); 2. in cc ph tr (CE) bng Pt; 3. Dung dch cht in li; 4. in cc so snh (RE)
- in cc bc; 5. ng h ampe; 6. in tr iu khin; 7. Ngun mt chiu; 8. My o th E(V).
152
2
i (A/cm )
1
2
E (V)
+
2
Hnh 8.4.
ng phn cc i - f(E)
Nhnh anot 1, 2; Nhnh catot 1, 2
ng 11 c dc cao hn ng 22.
T hnh v 8.4, trong khong th phn cc 10 mV so vi Em cho php xc nh c
trc tip im v trong khong ny quan h gia mt dng i v th E l tuyn tnh. Mt khc,
c th bng cch ngoi suy cc ng Tafel anot v catot (xem hnh 8.5) ti im giao nhau
ca cc ng ny ng vi th Em v lgim.
E (V)
z+
e
M
ng Tafel ant
ze
e+
M
Em
zH +
+z
e
ng Tafel catt z
2 H
2
lgi (A/cm2)
lgim
Hnh 8.5
ng cong phn cc ca kim loi Me (v d thp) trong mi trng axit (v d HCl)
d ( E )
Rp = = (8.9
di m
im
E (V)
Me - ze Me z+
E i
E m
zH + + ze z H
2
2
Hnh 8.7
ng cong phn cc E - f(i)
Ngoi nhng phng php in ho nu trn, ngy nay ngi ta cn dng cc phng
php khc nghin ci v n mn - phng php tng tr. Vn ny s c cp n
trong sch chuyn kho v cc phng php o in ho.
156
Ph lc
1 Li+ + e = Li 3,024
2 Cs+ + e = Cs 3,020
4 Rb+ + e = Rb 2,990
8 K+ + e = K 2,924
9 Ra2+ + 2e = Ra 2,920
10 Ba2+ + 2e = Ba 2,900
11 Sr2+ + 2e = Sr 2,890
12 Ca2+ + 2e = Ca 2,870
15 Na+ + e = Na 2,714
20 Ce3+ + 3e = Ce 2,480
157
21 Nd3+ + 3e = Nd 2,440
23 Sm3+ + 3e = Sm 2,410
24 Gd3+ + 3e = Gd 2,400
26 La3+ + 3e = La 2,370
27 Y3+ + 3e = Y 2,370
28 H2 AlO3 + H2O + 3e = Al + 4OH 2,350
29 Mg2+ + 2e = Mg 2,340
31 Am3+ + 3e = Am 2,320
34 Lu3+ + 3e = Lu 2,25
1
35 H2 + e = H 2,23
2
38 H+ + e = H(r.) 2,10
39 Sc3+ + 3e = Sc 2,08
40 Pu3+ + 3e = Pu 2,07
41 AlF63 + 3e = Al + 6F 2,07
42 Th4+ + 4e = Th 1,90
158
43 Np3+ + 3e = Np 1,86
44 H2PO2 + e = P + 2OH 1,82
45 U3+ + 3e = U 1,80
48 Ti2+ + 2e = Ti 1,75
49 SiO32 + 3H2O + 4e = Si + 6OH 1,73
50 HPO24 + 2H2O + 3e = P + 5OH 1,71
51 Hf4+ + 4e = Hf 1,70
52 Be2+ + 2e = Be 1,70
54 Al3+ + 3e = Al 1,67
55 HPO32 + 2H2O + 2e = H2PO2 + 3OH 1,65
57 Zr4+ + 4e = Zr 1,53
60 ZnS + 2e = Zn + S2 1,44
70 CdS + 2e = Cd + S2 1,23
71 H2GaO3 + H2O + 3e = Ga + 4OH 1,22
72 ZnO22 + 2H2O + 2e = Zn + 4OH 1,216
73 CrO2 + 2H2O + 3e = Cr + 4OH 1,20
74 SiF62 + 4e = Si + 6F 1,20
75 TiF62 + 4e = Ti + 6F 1,19
77 V2+ + 2e = V 1,18
78 16H2O + HV6O17
3
+ 30e = 6V + 33OH 1,15
81 Nb3+ + 3e = Nb 1,10
82 NiS ( ) + 2e = Ni + S2 1,07
84 BF4 + 3e = B + 4F 1,06
85 Mn2+ + 2e = Mn 1,05
86 PO34 + 2H2O + 2e = PO32 + 3OH 1,05
160
89 WO24 + 4H2O + 6e = W + 8OH 1,05
92 FeS() + 2e = Fe + S2 1,01
94 PbS + 2e = Pb + S2 0,98
105 SO24 + H2O + 2e = SO32 + 2OH 0,90
112 2NO3 + 2H2O + 2e = N2O4 + 4OH 0,85
UO22+ + 4H + 6e = U + H2O
+
117 0,82
123 HSnO2 + H2O + 2e = Sn + 3OH 0,79
130 CrCl2+ + 3e = Cr + 2Cl 0,74
162
Au ( CN )2 + e = Au + 2CN
151 0,60
2
152 AsS34 + 2e = AsS2 + 2S 0,60
163
154 Re O4 + 2H2O + 3e = ReO2 + 4OH 0,594
157 Re O4 + 4H2O + 7e = Re + 8OH 0,584
159 2SO3 + 3H2O + 4e = S2O32 + 6OH 0,58
166 O2 + e = O2 0,56
178 S + 2e = S2 0,508
184 NO2 + H2O + e = NO + 2OH 0,46
8 8
190 CdSO4. 3H2O + 2e = Cd + SO24 + H2O 0,435
3 3
1
218 HCNO + H+ + e = (CN)2 + H2O 0,27
2
228 HO2 + H2O + e = OH + 2OH 0,24
264 CuI2 + 2e = Cu + 2I 0,0
268 NO3 + H2O + 2e = NO2 + OH 0,01
269 HOsO5 + 4H2O + 8e = Os + 9OH 0,02
271 SeO24 + H2O + 2e = SeO32 + 2OH 0,03
275 CuBr2 + e = Cu + 2Br 0,05
Re O4 + 8H + 7e = Re + H2O
+
298 0,15
299 2NO2 + 3H2O + 4e = N2O + 6OH 0,15
307 CuCl2 + e = Cu + 2Cl 0,19
S2O62 + 4H + 2e = 2H2SO3
+
310 0,20
UO22+ + 4H + 2e = U
+ 4+
335 + 2H2O 0,334
3 4
340 Fe ( CN )6 + e = Fe ( CN )6 0,36
345 HgCl24 + 2e = Hg + 4Cl 0,38
351 FeF63 + e = Fe
2+
+ 6F 0,4
Re O4 + 4H + 3e = ReO2 + 2H2O
+
370 0,51
371 ClO4 + 4H2O + 8e = Cl + 8OH 0,51
173
377 I2 + 2e = 2I 0,534
378 I3 + 2e = 3I 0,535
379 BrO3 + 2H2O + 4e = BrO + 4OH 0,54
392 MnO24 + 2H2O + 2e = MnO2 + 4OH 0,58
393 PtBr42 + 2e = Pt + 4Br 0,58
174
396 OsCl36 + 3e = Os + 6Cl 0,60
397 PdBr42 + 2e = Pd + 4Br 0,60
398 RuCl52 + 3e = Ru + 5Cl 0,60
403 ClO3 + 3H2O + 6e = Cl + 6OH 0,62
UO22+ + 4H + 2e = U
+ 4+
405 + 2H2O 0,62
406 PtBr6 + 2e = PtBr4 + 2Br 0,63
Au ( CNS )4 + 2e = Au ( CNS )2 + 2CNS
410 0,645
Au ( NCS )4 + 3e = Au + 4NCS
414 0,66
175
421 Au ( NCS )2 + e = Au + 2NCS 0,69
427 IrCl36 + 3e = Ir + 6Cl 0,72
428 PtCl24 + 2e = Pt + 4Cl 0,73
NpO2+ + 4H + e = Np
+ 4+
434 + 2H2O 0,75
449 AuBr4 + 3e = Au + 4Br 0,87
450 2IBr2 + 2e = I2 + 4Br 0,87
451 HO2 + H2O + 2e = 3OH 0,88
NO3 + 4H + 3e = NO + 2H2O
+
459 0,96
460 AuCl4 + 2e = AuCl2 + 2Cl 0,96
461 AuBr2 + e = Au + 2Br 0,96
470 AuCl4 + 3e = Au + 4Cl 1,00
+
V ( OH )4 + 2H + e = VO + 3H2O
+ 2+
471 1,00
VO34+ + 6H + e = VO
+ 2+
476 + 3H2O 1,031
PuO22+ + 4H + 2e = Pu
+ 4+
477 + 2H2O 1,04
1
479 ICl2 + e = 2Cl + I2 1,06
2
178
486 AuCl2 + e = Au + 2Cl 1,13
PuO2+ + 4H + e = Pu
+ 4+
487 + 2H2O 1,15
1
IO3 + 6H + 5e =
+
494 I2 + 3H2O 1,195
2
AmO2+ + 4H + e = Am
+ 4+
505 + 2H2O 1,26
N2H4 + 4H + 2e = 2NH4+
+
506 1,275
1
CrO4 + 8H + 7e =
+
513 Cr2 + 4H2O 1,34
2
1
523 HIO + H+ + e = I2 + H2O 1,45
2
1
ClO3 + 6H + 5e =
+
525 Cl2 + 3H2O 1,47
2
MnO4 + 8H + 5e = Mn
+ 2+
531 + 4H2O 1,51
1
BrO3 + 6H + 5e =
+
532 Br2 + 3H2O 1,52
2
1
534 HBrO + H+ + e = Br2 + H2O 1,59
2
AmO22+ + 4H + 3e = Am
+ 3+
545 + 2H2O 1,69
AmO2+ + 4H + 2e = Am
+ 3+
548 + 2H2O 1,725
FeO24 + 8H + 3e = Fe
+ 3+
551 + 4H2O 1,9
554 OH + e = OH 2,0
560 F2 + 2e = 2F 2,65
K hiu
i H s Vanhof dn in ring
K Hng s in li C in dung lp kp
G Bin thin th ng t S ti
nhit ng p
t+ S ti cation
Ha th E Th in cc