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An Mon KL PDF
An Mon KL PDF
n mn v bo v kim loi
Trnh Xun Sn
Mc lc
Chng 1 Phn m u ......................................................................................................... 5
1.1
1.2
1.3
1.3.1
1.3.2
1.3.3
M u ..................................................................................................................... 14
1.5
2.2.1
dn in ring ................................................................................................. 14
2.2.2
dn in ng lng..................................................................................... 15
1.6
1.7
1.8
1.9
S vn ti.................................................................................................................. 22
1.10
3.2
Lp in kp trn b mt in cc ........................................................................... 28
3.3
S ph thuc ca gi tr th in cc vo nng cht phn ng, phng trnh
Nernst 30
3.4
3.4.1
in cc loi 1 ..................................................................................................... 32
3.4.2
in cc loi 2 ..................................................................................................... 33
3.4.3
in cc kh ......................................................................................................... 36
3.4.4
3.4.5
3.5
3.6
3.6.1
3.6.2
Sc in ng ca pin in .................................................................................. 43
3.6.3
3.7
M u ..................................................................................................................... 50
4.2
1.10.1
1.10.2
1.10.3
4.3
5.1
5.1.1
in cc n v s phn cc ............................................................................... 62
5.1.2
in cc phc tp - in cc hn hp ................................................................. 62
5.2
5.3
5.4.1
5.4.2
5.5
5.6
5.7
5.7.1
5.7.2
5.7.3
n mn u ............................................................................................................ 104
1.12
n mn cc b ....................................................................................................... 104
1.12.1
1.12.2
1.13
1.14
6.5.1
6.5.1
6.5.1
n mn mi........................................................................................................ 117
6.5.1
6.5.1
n mn mi mn................................................................................................ 118
6.5.1
n mn do ma st............................................................................................... 118
1.15
6.5.1
6.5.2
6.5.3
6.5.4
6.5.5
6.5.6
7.1.1
7.1.2
7.1.3
7.1.4
7.1.5
7.1.6
7.1.7
7.2
Lp ph v c .................................................................................................... 139
7.3.3
Lp ph hu c .................................................................................................. 141
7.3.4
7.4
Bo v kim loi chng n mn kim loi bng phng php in ho ................... 142
7.4.3
Bo v anot......................................................................................................... 146
M u ................................................................................................................... 147
8.2
Chng 1
Phn m u
1.1 nh ngha v s n mn kim loi
Cm t n mn c dch ra t ch corrosion, n xut pht t t ng latin
corrodre c ngha l gm nhm hoc ph hu. V ngha rng s n mn c dng
ch cho s ph hu vt liu trong bao gm kim loi v cc vt liu phi kim loi khi c s
tng tc ho hc hoc vt l gia chng vi mi trng n mn gy ra. C th n c mt
s hin tng n mn sau:
S chuyn ho thp thnh g thp khi thp tip xc vi khng kh m.
S rn nt ca ng thau, kim loi ng khi tip xc vi mi trng amoniac.
S lo ho ca cc vt liu polyme do tc dng ca tia cc tm, do tc dng ca dung
mi, ca nhit v.v...
S n mn thu tinh do mi trng kim gy ra v.v...
y chng ta ch quan tm n vn n mn kim loi, v kim loi l vt liu c s
dng ph bin nht trong cc ngnh cng nghip, n c mt s u im hn hn cc vt liu
khc:
dn nhit, dn in cao;
bn c hc cao, co gim, khng ko cao;
bn nhit cao.
v c bit t n d dng ch to ra cc thit b, my mc v.v... Do nhng tnh u vit vn c
ca kim loi cho nn kim loi xm nhp vo hu ht cc ngnh cng nghip c dng
ch to cc thit b, cc cu kin, my mc trong cc ngnh sau y: c kh ch to my; cng
nghip nng lng - cc nh my nhit in; nh my in nguyn t; cng nghip quc
phng - ch to v kh; cng nghip hng khng - ch to my bay; giao thng vn ti - ch
to cc phng tin giao thng: tu bin, t, xe ho, cu cng v.v...; cng nghip xy dng:
xy dng nh, c bit nh cao tng ti cc khu ven bin, cc cu cng; v cng nghip du
kh - cc thit b khai thc v ch bin du kh v.v...
S n mn y ngm hiu l n mn kim loi do tc ng ho hc hoc vt l ca mi
trng xm thc lm suy gim tnh cht ca vt liu lm gim cht lng, gim thi gian khai
thc ca cc my mc, thit b v cu kin, v ng nhin gy ra tn tht ln i vi nn
(1.1)
Trong mi trng dung dch, axit HCl v mui FeCl2 c k hiu l axit HCl(l); FeCl2(l)
tn ti dng ion. Vy c th vit:
Fe + 2H+ + 2Cl Fe2+ + 2Cl + H2
(1.2)
Trong trng hp trn, cht oxi ho l proton H+ b xonvat ho. Nhng sn phm ca
phn ng l ion Fe2+ b xonvat ho v kh H2. Cc ion Cl khng trc tip tham gia phn ng,
vy (1.2) c vit dng n gin:
Fe + 2H+ Fe2+ + H2
(1.3)
Trong mi trng kim v trung tnh, s n mn kim loi l phn ng xy ra gia kim
loi v oxi. V d trong khng kh m, st b n mn to ra g st dng FeOOH theo phn ng:
4Fe + 3O2 + 2H2O 4FeOOH
(1.4)
phn ng anot
2H+ + 2e H2
phn ng catot
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.
(1.6)
= ZF
dn i
dt
=I
(1.7)
hoc
dn i
dt
dt
(1.8)
ZF
: tc phn ng (mol/s)
(1.9)
Trong pin ny, trn anot () kim loi km b oxi ho thnh ion Zn2+:
() anot:
Zn Zn2+ + 2e
(1.10)
Cu2+ + 2e Cu
(+) catot:
(1.11)
(1.12)
Khi mch pin (1.9) khp kn th sinh ra dng in do electron di chuyn t anot n catot.
Trong pin (1.9) anot Zn c tham gia phn ng chuyn kim loi Zn thnh ion Zn2+ i vo dung
dch.
Pin hiro v oxi (xem hnh 1.1) c to thnh hai in cc hiro Pt(H2) H+ v in cc
oxi Pt(O2) H+.
() Pt(H2) H+ (O2) Pt (+)
(1.13)
2
1
Hnh 1.1
Pin hiro oxi
1. Dung dch axit H3PO4 hoc H2SO4;
2H2 4e 4H+
(1.14)
(+) catot:
O2 + 4H+ + 4e 2H2O
(1.15)
I = 4F
dnO2
dt
= 2F
dn H2
dt
(1.16)
10
2H2O O2 + 4H+ + 4e
() catot:
4H+ + 4e 2H2
O2
H2
Hnh 1.2
Bnh in phun nc iu ch H2 v O2
b
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
1
Hnh 1.4
Pin n mn Fe - Pt
12
13
g
Hnh 1.5
Cc dng n mn thng gp trong thc t
14
Chng 2
S n in ca dung dch cht in li
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.
(2.1)
(2.2)
1 A
R S
(1.cm1)
(2.3)
Khc vi cht dn in kim loi, dn in ring ca cht dn in loi 2 tng khi tng
nhit .
t = 18[1 + k(t 18oC)]
trong : t dn in ring nhit t bt k, toC > 18oC;
18 dn in ring nhit 18oC.
(2.4)
15
2.2.2 dn in ng lng
dn in ng lng ca dung dch cht in li kho st l dn in ca mt
dung dch cha ng mt ng lng gam cht in li c t gia hai in cc platin
song song vi nhau v cch nhau 1 cm.
Gia dn in ng lng v dn in ring c quan h vi nhau theo phng
trnh:
=
1000.
(2.5)
1
C
(2.6)
Vy:
Suy ra:
(2.7)
(2.8)
Hnh 2.1
S ph thuc ca dn in ng lng vo pha long V
16
(2.9)
Tc chuyn ng ca anion:
V = Vo.E (cm/giy)
(2.10)
cm
Khi E = 1 (V/cm) th U = Uo v V = Vo
= cm 2 / V.s
s.(v
/
cm)
trong : C/ =
+ = C/ + NA.Uo.E
(2.11)
= C/ NA.Vo.E
(2.12)
C
1000
Hnh 2.2
S di chuyn ca cc ion di tc dng ca in trng
trong :
+ = C + NA.Uo.E.103
(2.13)
= C NA.Vo.E.103
(2.14)
- phn li;
+, - s cation v anion;
17
NA
- l s Avogaro.
(2.15)
Q = C NA e.103.E (+ Z+ Uo + Z Vo)
(2.16)
(2.17)
(2.18)
(2.19)
Mt khc, ta c:
=
1000.
Cd lg/ l
= F (Uo + Vo)
(2.20)
(2.21)
V = F . Vo
(2.22)
Kt hp (2.22) v (2.20) ta c:
= (U + V)
(2.23)
(2.23a)
(2.24)
18
( .cm2.lg1)
1
HCl
CH3COONa
NaCl
426,00
91,00
126,50
H
O
H
O
H
+
O + H
H
O
H3+ O
Na+
K+
NH4+
Ca2+
349,8
50,1
73,5
73,5
59,5
OH
ClO4
HCO3
SO24
197,6
55,4
67,3
64,6
80
2+
Zn
52,8
i vi ion OH
H
O
H
O
H
O
H
O
19
Gi tr linh
U (H+)
Nng
25oC
H+
Dung mi 25oC
Nhit
H2O
C2H5OH
0 oC
50oC
0,01N
0,1N
349,8
62
240
465
338,9
325,5
Trong dung mi nc
2..C.N A
1000
= const .C
(2.25)
.C
1000
( + + )
= ( + + )
(2.26)
(2.27)
Kt hp vi (2.24) ta c:
=
(2.28)
20
Hnh 2.3
S ph thuc ca dn in ring vo nng C
(2.29)
(2.30)
trong :
I l hiu ng km hm in di do s tng tc tnh in ca lp v ion ngc du vi
ion trung tm b dch chuyn di tc dng ca in trng ngoi. Theo Onsage hiu ng km
hm I t l vi cn bc hai nng C .
II l hiu ng km hm phc hi cn li gi l hiu ng bt i xng. S tn ti ca
hiu ng ny l do s tng tc ca mt phn lp v kh quyn ion c in tch tri du cha
b ph v hon ton vi ion trung tm b dch chuyn di tc dng ca in trng ngoi.
Hiu ng II cng t l vi C v nht.
Phng trnh (2.30) c th vit:
= a C
(2.31)
Phng trnh (2.31) ch p dng cho dung dch cht in li mnh c nng khng vt
qu 102 lg/l.
21
(2.32)
Phng trnh (2.32) tng t phng trnh (2.24) p dng cho dung dch cht in li yu
v cng c gi l nh lut chuyn ng c lp ca ion.
T s gia dn in ng lng ca cht in li mnh ti nng cho trc so
vi dn in ng lng ti hn gi l h s dn f. i lng ny c trng cho
s tng tc gia cc ion.
f =
+ +
(2.33)
+ +
1-1
1-2
1-3
Gi tr f
0,8
0,75
0,4
22
Hnh 2.4
S ph thuc ca dn ng lng vo nng C
Hnh 2.5
S ph thuc ca dn in in ng lng vo
C lg/l
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:
=
trong :
g
a
I.t
96493
(2.34)
23
I.t
Z 96493
A I.t
Z
(2.35)
Khi in phn, cc ion chuyn in tch, lng in i qua cc in cc lun lun bng
nhau, nhng mi loi ion chuyn in khng ging nhau v tc chuyn ng ca chng
khc nhau.
Phn in do cation hoc anion ti i trong qu trnh in phn gi l s ti t.
S ti cation l:
t+ =
Uo
U o + Vo
+
+ +
U
U+V
(2.36)
Uo
U
=
=
U o + Vo
U+V
+ +
t+ + t = 1
Vy
(2.37)
(2.38)
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).
Gi thit tc tuyt i cation Uo v anion Vo l
Uo
Vo
2
3
Uo
Vo
0,01.2
0,01.3
2
3
(2.39)
Mt khc:
n = na + nc
(2.40)
T (2.39) v (2.40) ta c:
t+ =
v
t =
Uo
U o + Vo
Uo
U o + Vo
=
=
n a
n
n c
n
(2.41)
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)
25
Hnh 2.7
S mch o dn in ca dung dch cht in li
Cc in tr R1 v R2 c chn trc c
R1
R2
I1 Rx = I2 R2
RM
Vy
Rx
R1
R2
= 1 RM = Rx
A
S
1
Rx
A
S
K
Rx
(2.43)
26
1000.
S
S=
1000.
(2.44)
H + OH = HOH
(2.45)
(2.46)
27
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
28
Chng 3
Th in cc v sc in ng ca pin in
3.1 in cc v nguyn nhn sinh ra th in cc
in cc l mt h in ha gm cht dn in loi 1 tip xc vi cht dn in loi 2.
V d: Kim loi Cu tip xc vi dung dch mui sunfat ng Cu2+SO4/Cu hoc Cu2+/Cu
hoc Zn2+/Zn; Fe3+,Fe2+/Pt vv (mt gii hn gia hai pha rn v lng c k hiu bng
gch cho / hoc l gch thng).
V mt ha hc tm phn ra in cc tr v khng tr. Mt in cc c gi l in cc
tr nu dy dn loi 1 khng tham gia phn ng v ch c chc nng l trao i electron, v d
in cc Pt trong cc h in phn dung dch NaOH, dung dch H2SO4 Ngc li, mt in
cc gi l khng tr nu cht dn in loi 1 c tham gia phn ng oxi ho kh trn mt gii
hn pha v sau mt thi gian lm vic khng cn nguyn vn nh lc ban u
V d: Anot Ni trong cc qu trnh m in. in cc Ni b ha tan theo phn ng:
Ni 2e Ni2+
Sau thi gian phn ng khi lng anot niken b gim i v b chuyn thnh ion Ni2+
i vo dung dch.
Trn b mt gii hn ca hai pha cht dn in loi 1 v 2 lun tn ti lp in kp v n
l nguyn nhn sinh ra th in cc
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
30
Hnh 3.2
a) Lp kp c tnh n chuyn ng nhit;
b) S phn b th E(V) theo chiu dy lp kp
(3.1)
Khi i = 1 ta c:
Oxi + Ze U Redi
(3.2)
(3.3)
(3.4)
31
U = C SP
(3.5)
Ta c:
o
U = Cu
+ e Cu
2 + + RTln a
Cu2 +
o
U = Cu
= ZFE
2 + + 2e Cu + RTln a
Cu2 +
Vy th in cc E bng:
E=
o
Cu
2 + + 2 e Cu
ZF
RT
E = Eo +
o
trong : E =
ZF
RT
ZF
lg aCu2 +
(3.6)
lg aCu2 +
o
Cu
2 + + 2 e Cu
ZF
RT
E = Eo +
0,059
ZF
ln
i
a oxi
(3.7)
i
a Re
di
hoc 25oC ta c:
Z
lg
i
a oxi
(3.8)
i
a Re
di
Zn
= EoZn2 +
0,059
2
Zn
lg
a Zn2 +
a Zn
Fe2 +
o
= EFe
3+
+
Fe2 +
0,059
1
lg
aFe3 +
aFe2 +
25oC:
32
EO2
=
H2O
o
EO
2
+
H2O
0,059
4
lg
pO2 .a4H+
a2H2O
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 ...
T cc phng trnh (3.6), (3.7), (3.8) cho thy rng, mun xc nh gi tr th in cc E
cn phi bit chnh xc nng cc cht tham gia phn ng v gi tr th in cc tiu chun
Eo.
Gi tr th in cc tiu chun Eo ca mt in cc bt k c xc nh da vo th in
cc tiu chun hiro c gi tr chp nhn bng 0,00 V. V d th in cc tiu chun ca in
cc km: Zn2+/ Zn c gi tr bng 0,76 V NHE, c ngha l n c so vi th ca hiro
(v in cc hiro s c cp n trong phn sau) hoc vi in cc ng Cu2+/Cu c gi
tr th tiu chun bng 0,34 V NHE; qua nhng v d ta c th nh ngha gi tr th in
cc tiu chun Eo nh sau: "Gi tr th in cc tiu chun Eo ca mt in cc bt k cn xc
nh l sc in ng E ca pin in gm in cc tiu chun hiro ( aH+ = 1 v PH2 = 1
atm) v in cc tiu chun ca in cc cn xc nh". Du ca gi tr th in cc tiu
chun chp nhn l du dng so vi in cc tiu chun hiro nu trong pin in, in cc
tiu chun cn xc nh l cc dng (catot) so vi in cc tiu chun hiro v ngc li.
Trn c s o gi tr th in cc tiu chun ca cc in cc ngi ta xp cc gi tr th in
cc tiu chun thnh bng (xem bng 3.1) gi l bng gi tr th in cc tiu chun.
Nng cc cht phn ng ca in cc thng c biu din qua i lng hot a
ca cc ion tham gia phn ng, trong trng hp dung dch long th hot a ca cht phn
ng c thay bng nng C (mol/l).
V d i vi in cc Fe2+/Fe vi phn ng in cc l:
Fe2+ + 2e U Fe
25oC vi CFe 2 + = 106 mol/l th ta c gi tr th in cc ca cp Fe2+/Fe l:
EFe2 +
hoc
3.4
EFe2 +
Fe
o
= EFe
2+
+
Fe
= 0,441 +
Fe
0,059
2
0,059
2
lg
CFe2 +
CFe
lg 10 6 = 0,618 V
Phn loi in cc
3.4.1 in cc loi 1
33
(3.9)
Me
= EoMen +
0,059
Me
lg
a Men +
25oC
a Me
(3.10)
EZn2 +
EZn2 +
Zn
= EoZn2 +
0,059
Zn
0,059
= 0,76 +
Zn
a Zn2 +
lg
a Zn
lg a Zn2 +
ECu2 +
ECu2 +
Cu
o
= ECu
2+
0,059
Cu
= 0,34 +
0,059
2
Cu
lg
aCu2 +
aCu
lg aCu2 +
EFe2 +
EFe2 +
Fe
o
= EFe
2+
+
Fe
= 0,441 +
Fe
0,059
2
0,059
2
lg
aFe2 +
aFe
lg aFe2 +
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
C Ag =
TAgCl
CCl
EAgCl
= EoAgCl
EAgCl
Ag
hoc
EAgCl
Ag
Vy
EAgCl
Ag
0,059
1
Ag
Ag
EoAgCl
0,059
Ag
Ag
trong :
= EoAg +
0,059
Ag
lg C Ag +
lg TAgCl 0,059 lg CCl (3.11)
lg TAgCl
Gi tr th (V) v NHE
0,2384
0,2900
0,2890
EMex X y
Me
Me
0,059
y
(3.12)
lg a y
X
hoc
EHg 2Cl2
Hg
Hg
o
= EHg
2Cl 2
Hg
0,059 lg CCl
(3.13)
thuc
ca
gi
tr
th
in
cc
calomen
35
0,1N
EHg 2Cl2
1,0N
EHg 2Cl2
Bo ha
EHg 2Cl2
8
6
4
3
2
2
1
Hnh 3.3
Hnh 3.4
Cu to in cc bc
S in cc calomen
= 0,6156
Hg
0,059
2
lg CSO2
4
(3.14)
36
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.
H2
3
2
H2
Hnh 3.5
S in cc kh hiro
1. Platin; 2. Dung dch Hx+
3. Cu ni
E2H+
=
H2
o
E2H
+
+
H2
0,059
2
lg
a2H+
PH2
(3.15)
37
E2H+
H2
o
= E2H
+
= 0,0000 V
H2
= 0,059pH
(3.16)
H2
hoc t rH = lg PH2 ta c:
E2H+
= 0,059 + 0,0295rH
(3.17)
H2
(3.18)
= 0,401 V (NHE)
o
EO
2
OH
(3.19)
= 1,229 V (NHE)
H2O
= 0,401 + 0,059 lg
OH
PO1 2/ 4
(3.20)
aOH
i vi phn ng (3.19):
o
EO
2
H2O
1/4
(3.21)
38
Hai phng trnh (3.20) v (3.21) l tng ng nhau nu thay th hot OH aH2 =
KW
a H+
10 14
a H+
(3.22)
H2O
Fe3+ + e U Fe2+
Phng trnh Nernst tnh th in cc:
EFe3 +
hoc
Fe2 +
o
= EFe
3+
Fe
Fe2 +
= 0,771 +
EFe3 +
0,059
0,059
1
2+
lg
lg
aFe3 +
aFe2 +
aFe3 +
(3.23)
aFe2 +
EOx
Re d
o
= EOx
0,059
Z
Re d
lg
aOx
(3.24)
a Re d
(3.25)
hoc
Mn2 +
EMnO ,H+
4
3.4.5
EoMnO ,H+
4
+
Mn2 +
0,059
5
lg
a MnO .a8H+
4
a Mn2 + .a4H2O
a MnO
a Mn2 + .a4H2O
39
Phn ng in cc:
MexOy + yH2O +2ye U xMe + 2yOH
(3.26)
o
= ESb
2O3
0,059 lg aOH
Sb,OH
(3.27)
3 .H
Sb
o
ESb
+
2O3 .H
0,059
Sb
lg
aSb2O3 .a6H+
2
aSb
.a3H2O
3 .H
o
= ESb
O .H+
Sb
0,059pH
(3.28)
Sb
Hg,OH
o
= EHgO
+
Hg,OH
0,059
2
lg
aHgO
aHg .a2OH
Nu aHgO = 1, aHg = 1 th ta c:
EHgO
Hg,OH
o
= EHgO
Hg,OH
0,059 lg aOH
(3.29)
40
= 1,61 + 0,059 lg
Ce3 +
aCe4 +
(3.30)
aCe3 +
Fe3+ + e U Fe2+
= 0,77 + 0,059 lg
Fe2 +
aFe3 +
(3.31)
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:
1,61 + 0,059 lg
aCe4 +
= 0,77 + 0,059 lg
aCe3 +
vi
Kcb =
aCe3 + .aFe3 +
aCe4 + .aFe2 +
aFe3 +
aFe2 +
= 1014
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
EFe2 +
= 0,4402 +
0,059
2
Fe
lg aFe2 +
(3.32)
Cu2+ + 2e U Cu
ECu2 +
= 0,3370 +
Cu
0,059
2
lg aCu2 +
(3.33)
41
0,059
Kcb =
2
aFe2 +
aCu2 +
lg aFe2 + = 0,3370 +
0,059
2
lg aCu2 +
= 1026
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
Fe2+ = 1 th hot ca ion Cu2+ = 1026, khi trong dung dch nng ion Cu2+ rt nh.
2+
o
ENa
+
= 2,71 V, khi
Na
1
2
H2
= 0,37 V, khi
EoTi3 +
Ti
2+
1
2
H2
Cu +
1
2
1
2
o
( EFe
2+
= 0,44 V)
Fe
o
( ECu
2+
= 0,34 V)
Cu
mt nhit ng hc v lm phn hy nc gii phng oxi. V d trong dung dch cha ion
o
Ce4+ ( ECe
= 1,61 V) d dng chuyn thnh ion Ce3+ v gii phng hiro theo phn ng:
4+
Ce3 +
Ce4+ +
1
2
H2O = Ce3+ + H+ +
1
4
O2
42
Fe
o
khi bit EFe
2+
o
= 0,44 V v EFe
3+
Fe
Fe
Fe
Go3
3e
2e
Go2
1e
= 0,77 V. tnh c gi tr
2+
Fe3+
Go1
Fe2+
Da vo chu trnh trn ta c:
G3o = G2o + G1o
v suy ra:
3FE3o = 2FE2o + FE1o
3E3o
= 2E2o + E1o
E3o
o
EFe
3+
Vy
hoc
o
EFe
3+
=
Fe
2E2o + E1o
3
Fe
o
2EFe
2+
Fe
o
+ EFe
3+
Fe2 +
= 0,036 V
43
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:
Zn 2e Zn2+
Cu2+ + 2e Cu
;
;
EoZn2 +
o
ECu
2+
= 0,76 V
Zn
= + 0,34 V
Cu
(3.34)
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)
(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:
= o +
RT
ZF
lg
a Zn .aCu2 +
a Zn2 + .aCu
(3.37)
44
Phn ng 25oC th ta c:
= o +
0,059
lg
a Zn .aCu2 +
a Zn2 + .aCu
= +
Vy
ZF
lg
1
a Re2 d .aOx
2
'
1'
aOx
.a Re2 d
2
1
o
Vi iu kin th in cc tiu chun EOx
1
Re d1
(3.38)
o
> EOx
2
Cu
EoZn2 +
0,059
2
lg
aCu2 +
(3.39)
a Zn2 +
1
2
Gi tr sc in ng 25oC l:
= o 0,059lgK +
0,059
= o 0,059lg1014 +
lg PH2 .PO1 2/ 2
0,059
2
lg PH2 .PO1 2/ 2
(3.40)
45
(3.41)
RT
2F
RT
F
lg aCd2 + .aSO2
4
lg a CdSO4
(3.42)
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:
= o +
0,0591
= 1,1 +
0,0591
lg
lg
a Cu2+
a Zn2+
a Cu2+
a Zn2+
Khi pin nm trng thi cn bng th hng s cn bng Kcb ca phn ng c tnh:
1,1 =
0,0591
2
lgKcb
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
() Ag
(+) Ag+(a2) + 1e Ag
Ag+ (a2)
Ag+ (a1)
Qu trnh pin hot ng gn lin vi s gim hot Ag+ ti khu catot v tng hot
Ag+ ti vng anot. Pin khng hot ng khi hot Ag+ ti hai vng catot v anot bng nhau.
Sc in ng:
RT
F
lg
a2
a1
= 0,0591lg
Khi nng
a2
a1
v 25oC.
a2
a1
= 10 th sc in ng E = 0,0591 (V).
47
cquy AB
x AK
Vy:
acquy
E
AB
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:
x = cquy.
AB
(a)
AK
cquy = w.
AB
AB
AK AK '
(b)
AK
AK
= 1,018.
(V)
AK '
AK ' AB
AB
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
Cu + Zn2+
(c)
G = 2Fo = 2 96493. o
(3.44)
= S hoc 2F
T p
Vy:
G = H T2F
hoc:
2Fo = H T2F
o =
(3.45)
= S
T p
T p
(3.46)
(3.47)
T p
H
2F
T p
+T
(3.48)
ng
.
T p
ra
2F
T p
o =
(3.49)
trong Qp gi l nhit phn ng. Phng trnh (3.49) cho bit quan h gia sc in
ng v nhit phn ng.
49
= 0 th ton b nhit phn ng chuyn thnh cng in v
< 0 th ch
T p
T p
Nu
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.
> 0 th cng in thu c ln hn nhit phn ng chuyn thnh cng.
T p
Nu
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.
Ghp cc in cc to thnh pin in 25oC:
() (Pt) H2 / 2Hx+ / Cl, AgCl / Ag+ (+)
o sc in ng ca pin ny ta c o v theo quy c ta c:
o = E(+) E()
hoc
o = 0,2222 V ( 0,0591pHx)
Vy:
pHx =
o 0,2222
0,0591
(3.50)
50
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.
V d:
Ox + ne
Red
Fe3+ + 1e U
Fe2+
(4.1)
0,059
n
lg
aOx
aRed
(4.2)
51
i vi (4.1):
0,059
1
hoc:
Khi t s
EFe3+ / Fe2+ = Eo +
aFe3+
aFe2+
lg
aFe3+
aFe2+
0,059
1
lg
aFe3+
aFe2+
(4.3)
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).
z
2
H2O U
MeOz/2 + zH+
(4.4)
V d:
Cu2+ + H2O U
CuO + 2 H+
azH+
z+
aMe
(4.5)
52
azH+ = K. aMez+
Vy:
pH =
lg
(4.6)
K.a Mez +
a2H+
K=
v
pH =
pH =
1
2
1
2
lg
aCu2+
= 1,45.108
1
1,45.10
lg1,45.108
1
2
1
2
lg
1
a Cu2 +
m
2
H2
(4.7)
V d:
Mn7+ + 8H+ + 5e U Mn5+ + 4H2O
trong :
(4.8)
j = /j = 1, j = Mn7+ v Mj = Mn5+
E=E +
E = Eo
hoc
RT
zF
RT
zF
ln
a j .a m
H+
j
/j
/2
a / .a m
H 2O
j
lnK 2,303
RT
zF
.m.pH
E = a bpH
(4.9)
trong :
a = Eo
25oC ta c: b = 0,059
m
z
RT
zF
lnK v b = 2,303
RT
zF
.m
53
m
n
( 25oC).
m
z
(4.10)
(4.11)
2H2O + 2e U H2 + 2OH
(4.12)
25 C:
E2H+ /H
o
= E2H
+
+
/H
2
0,059
2
lg
a 2H+
PH2
(4.13)
54
Hnh 4.2
Gin E - pH i vi h H2O, H+, OH, O2
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+
hoc
2H2O
(4.14)
O2 + 4e + 2H2O U 4OH
(4.15)
25oC:
E O2 / H 2 O =
hoc:
o
+
EO
2 / H2 O
lg a 4H+ . PO2
(4.16)
0,059
(4.17)
lg PO2
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
2
lg CFe2 + = 0,62 V
o
= + 0,77 V
Fe3+ + 1e U Fe2+ vi EFe
3+
/ Fe2 +
o
= 0,77 +
EFe
3+
/ Fe2 +
0,059
1
lg
CFe3 +
CFe2 +
/ HFeO2
(4.19)
= + 0,77 V
(4.18)
(4.20)
= 0,50 V
(4.21)
(4.22)
HFeO2 + H
U Fe(OH)2
pH = 12,30 (4.23)
56
(4.24)
o
E = EFe(OH)
+ 0, 059 lg C2H+
2 / Fe
(4.24a)
Vy:
(4.25)
E = + 0,27 0,059pH
Fe(OH)3 + 3H+ + 1e U Fe2+ + 3H2O
(4.26)
E = + 1,41 0,177pH
+
HFeO2 + 3H + 2e U Fe + 2H2O
(4.27)
E = 0,316 0,089pH
T cc phng trnh ph thuc ca th - pH ca h Fe - H2O ta v c gin th E pH (xem hnh 4.3).
Trn hnh 4.3, im bt k trn on thng (4.18) ng vi th
0,62 V v khng
ph thuc pH trong khong t 0 9,6 th hin trng thi cn bng ca phn ng Fe2+ + 2e U
Fe. Trong khong pH trn nu th m hn gi tr 0,62V th st trng thi bn vng v b n
mn vi tc rt nh ( CFe2 + < 106M). Vng S nm di ng abcd c gi l vng st
khng b n mn min dch n mn ca st.
57
Hnh 4.3
Gin th - pH i vi h Fe - H2O 25oC, P = 1 atm
(4.28)
58
ng vi th oxi ha kh 25oC:
0,059
E = 1,676 +
Vi
lg C Al3 +
C Al3 + = 10 M th E = 1,794 V
(4.28a)
(4.29)
Th oxi ho kh tng ng 25 C:
E = 1,563 0,059pH
(4.29a)
Trong vng kim Al b ho tan theo phn ng:
Al(OH)4 + 3e U Al + 4OH
(4.30)
E = 1,2 +
0,059
3
lg C( AlOH) 0,079pH
4
E = 1,32 0,079pH
(4.30a)
lg C Al3 +
Vi gi tr
pH = 2,44
Vi
(4.31)
(4.32)
pH = 16,53 + lg C Al(OH)
4
Vi
C Al(OH) = 10 M th pH = 10,53
(4.32a)
59
Hnh 4.4
Gin th E(V) - pH ca nhm 25oC vi C
Al3 +
=C
Al(OH)4
= 106
4.3.2.3 Gin th E - pH ca km
(4.33)
0,059
2
lg C Zn 2 +
Vi C Zn 2 + = 106M th:
E = 0,76 +
0,059
2
lg 106 = 0,937 V
(4.33a)
(4.34)
ng vi th cn bng:
o
EZn(OH)2 / Zn = E +
0,059
2
lg CZn(OH)2 .C2H+
E = 0,439 0,059pH
Trong vng kim cao km b ho tan to ra ion Zincat:
(4.34a)
60
ZnO2 + 4H + 2e U Zn + 2 H2O
(4.35)
Th cn bng:
o
E ZnO / Zn = E +
0,059
lg C ZnO . C2H+
2
(4.35a)
Trong min kim thp ion Zn2+ b chuyn thnh Zn(OH)2 theo phn ng:
Zn2+ + 2H2O U Zn(OH)2 + 2H+
(4.36)
Vy
hoc
lgKcb = 2pH + lg C Zn 2 +
pH = 8,439
(4.36a)
(4.37)
(4.37a)
61
Hnh 4.5
Gin th E(V) - pH ca km 25oC.
62
Chng 5
n mn in ha hc
5.1 Nhng khi nim c bn
5.1.1 in cc n v s phn cc
in cc n l mt h in ho gm cht dn in loi 1 tip xc vi cht dn in loi
2, trn mt gii hn pha ch xy ra mt phn ng in ha.
V d 1: Kim loi ng nhng vo CuSO4 khng cha oxi, khi phn ng in cc
(xem hnh 5.1.a):
Cu2+ + 2e U Cu
(5.1)
Fe3+ + 1e U Fe2+
(5.2)
E = = Ei Ecb
(5.3)
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:
(5.4)
(5.4a)
63
O2 + 2H + + 2e H2O
(5.5)
ngha l c th tn ti h oxi ha kh th 2 l:
1
2
O2 + 2H + + 2e U H2O
(5.5a)
1
2
O2 + 2H + Cu2+ + H2O
(5.6)
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).
64
Hnh 5.2
S n mn in ho ca kim loi t trong dung dch cht in li
(5.7)
Ion kim loi trn b mt in cc chuyn vo dung dch ng thi c electron d trn kim
loi.
Cc electron d vng anot c dch chuyn n vng catot trn b mt kim loi v ti
xy ra cc phn ng km theo:
Nu mi trng c ion H+ th xy ra phn ng gii phng hiro.
ZH+ + Ze
Z
2
H2
(5.8)
O2 + Ze + ZH+
Z
2
H2O
(5.9)
65
Trn catot v s gii phng hiro cng bao gm nhiu giai on sau:
a) Chuyn cc phn t tch in 3+ t trong th tch dung dch n lp dung dch phn
st b mt bng nhiu cch: hoc s khuch tn do chnh lch nng , hoc bng s in di,
hoc bng chuyn ng
i lu.
b) Giai on kh lp v xonvat ho ca phn t tch in 3+ .
c) Giai on phng in ca ion H+:
2H+ + 2e H2
d) Giai on hp ph ca sn phm Hhf trn b mt in cc.
e) Chuyn sn phm vo dung dch v.v....
Vy phn ng in ho xy ra trn mt gii hn pha ca qu trnh n mn kim loi ti
vng catot cng nh anot bao gm rt nhiu giai on, song giai on no chm nht s
khng ch ng hc ca ton b qu trnh.
Tu thuc vo kh nng phn ng ngha l phn cc ca in cc s quyt nh giai
on khng ch ng hc. Trong in ho cng nh qu trnh n mn in ho, ng hc ca
qu trnh thng c khng ch bi hai giai on chm nht:
S trao i electron ca cc phn t tch in trn b mt in cc xy ra chm nht v
khng ch ng hc trao i electron hoc cn gi l ng hc trao i in tch, ng hc
in ho.
S chuyn vt cht t dung dch n b mt in cc xy ra ch yu do s khuch tn
l giai on chm nht trong qu trnh in ho hoc n mn kim loi s l giai on khng
ch ng hc ca ton b qu trnh v thng gi l ng hc khuch tn.
c
ZZZX
Ox+ Ze YZZZ
Red
v
(5.10)
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.
I=
dq
dt
= ZFv
66
Ic = ZFvc
(5.11a)
Ia = ZFva
(5.11b)
I
S
Vy tc phn ng catot v anot c biu din qua mt dng tng ng l icv ia.
Tc phn ng in ho (5.10) c biu din nh sau:
i vi phn ng catot v anot:
G*c
RT
ic = ZF.kc.Cox.exp
G*a
ia = ZF.ka.CRed.exp
RT
(5.12a)
(5.12b)
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
G*a = G ZFE
(5.13)
(5.14)
RT
ia = ZFka.CRed.exp
hoc
G o
ZFE
exp
RT
RT
ia = ZFka.CRed.exp
ZFE
RT
ia = ZFKa.CRed.exp
trong :
(5.15)
(5.16)
G o
Ka = ka.exp
RT
Mt cch tng t:
ZFE
RT
ic = ZFKc.COx.exp
trong :
(5.17)
G o
RT
Kc = kc.exp
68
ZFEcb
RT
(5.18)
ZFEcb
RT
(5.19)
o
ic = ZFKc. COx
.exp
RT
Suy ra:
Ecb =
Vy:
Ecb = Eocb +
Khi
o
COx
CoRe d
ZF
ln
Kc
Ka
RT
ZF
ln
RT
ZF
ln
o
COx
(5.21)
CoRe d
o
COx
(5.22)
CoRe d
o
o
o
= ZFK so .COx
.CRe
io = ZFK1a .K c .CoRe d .COx
d
(5.24)
Vy
(5.25)
o
o1
i o = i oo .COx
.CRe
d
(5.26)
o
lg COx
lg i o
= v
lg Co
Re d
CoRe d
=1
o
COx
(5.27)
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)
CRe d
CoRe d
RT
RT
COx
(5.30)
t Ei Ecb = E = c gi l qu th v t (5.30) ta c:
ZF COx
ZF
C d
i = i o Re
exp
o exp
o
CRe d
RT COx
RT
(5.31)
ZF
ZF
i = i o exp
exp
RT
RT
(5.32)
o
o
RT CFe3 +
RT
CFe2 +
(5.33)
70
(trong t a =
RT
ZF
) v
a
a
(5.34)
>> 1 .
hoc
alnia = alnio + a
Vy
a = alnia = alnio
hoc
a = Aa + Balnia
(5.35)
(5.36)
A a = a ln i o v Ba = 2,303a .
trong :
Hnh 5.4
ng phn cc - s ph thuc ca mt dng in i (A/cm2) vo qu th (v).
Vy khi
a
a
(trong : c =
RT
ZF
) v
c
c
(5.37)
<< 1 .
c = Ac + Bc lgic
(5.38)
71
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
RT
F
th phng trnh(5.32) s c
dng:
i = io
hoc
ZF
RT
RT
ZFi o
(5.39)
.i = R p .i
(5.40)
trong
Rp =
RT
ZFi o
c gi l in tr phn cc
(5.41)
d
di
72
d
di
rt nh,
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)
ab - H phn cc l tng
d
di
d
di
73
O2).
(5.42)
Coi CSi
(5.43)
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
i = ZFDi
(5.44)
Coo CSi
(5.45)
74
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:
id = ZFDi
Coi
(5.46)
Cibh Coi
(5.47)
Cibh
(5.48)
H.
Khi phn cc catot trn in cc xy ra phn ng:
Cu2+ + 2e Cu
ECu2 +
Cu
o
= ECu
2+
+
Cu
RT
2F
o
ln CCu
2+
(5.49)
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:
E
Cu2 +
Cu
o
= ECu
2+
+
Cu
RT
2F
ln CsCu2 +
(5.50)
o
s
l nguyn nhn sinh ra chnh lch th v cn
S chnh lch nng C = CCu
2+ C
Cu2 +
75
c = Ei
Cu2 +
Cu
ECu2 +
=
Cu
RT
2F
ln
CsCu2 +
o
CCu
2+
(5.51)
=1
(5.52)
id
hoc
ln 1
2F
id
RT
(5.53)
2F
i = id 1 exp
c
RT
(5.54)
i = id 1 exp
c
RT
(5.55)
Hnh 5.8
S ph thuc ca mt dng i(A/m2) v phn cc catot (v)
RT
, khi phng trnh (5.55) c
F
dng:
i = id
hoc
i=
c
Rp
ZF
RT
(5.56)
5.57)
76
trong
Rp =
RT
(5.58)
ZFid
RT
F
i = id
CsCu2 +
o
CCu
2+
exp c
c
(5.60)
i
i c = i o 1 c
id
c
exp
(5.61)
77
i o exp c
c
ic =
i
1 o exp c
id
c
(5.62)
Nu c c gi tr rt ln th
ic
id
(5.63)
c
ZZZX
Z Fe
Fe2+ + 2e YZZZ
Fe Z
ia
(5.64)
78
iH
c
ZZZZ
X
2H + 2e YZZZ
Z H2
H+
(5.65)
ia
hoc
H2 O
ic
ZZZZ
X H2 + OH
2H2O + 2e YZZZ
H2 O Z
ia
(5.66)
ic
ZZZZ
X 2H2O
O2 + 4H+ + 4e YZZZ
O2 Z
ia
hoc
O2
ic
ZZZZ
X 4OH
O2 + 4e + 2H2O YZZZ
O2 Z
ia
(5.67)
(5.68)
c
ZZ
XZ Fe
Fe2+ + 2e YZZZ
iFe
(5.69)
c
2H + 2e ZZZZ
YZ
ZX H2
H+
(5.70)
ia
(5.71)
H
Fe
H
iFe
a + ia = i c + i c
(5.72)
+
Fe
H
H
th
Phng trnh (5.71) xy ra vi iu kin c s phn cc v iFe
a >> i c ; i c >> i a
phng trnh (5.72) c dng:
+
H
iFe
= im = i
a = ic
(5.73)
79
| iH
c |; khi phng trnh (5.71) ng vi trng thi n nh.
( )
ZF
Fe
= iFe
Eam Ecb
o exp
RT
( )
+
ZF
H+
= iH
(Em Ea )
o exp
RT
im = iFe
a
v
im = iH
a
Eam
Eam
(5.74)
(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
2. H 2H+ + 2e
U Fe
U Fe
3. H hn hp
hoc
ZF
ZF
Fe
Fe
iFe
Eam Ecb .exp
( Ei Eam )
a = i o exp
RT
RT
Kt hp vi (5.74) ta c:
(5.76)
80
ZF
iFe
(Ei Em)
a = im.exp
RT
(5.77)
(5.78)
ZF
ZF
exp
RT
RT
(5.79)
i = im exp
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.
Chp nhn = = 0,5 v khi c s phn cc rt nh | | <<
RT
ZF
c dng:
i = im.
ZF
RT
hoc:
Vy
Rp =
(5.80)
RT
= Rp.i
ZF i am
(5.81)
RT
d
=
ZF.iam
di =0
(5.82)
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.
Khi c s phn cc ln >>
RT
ZF
ia = im.exp
a =
RT
ZF
.2,303lgia
(5.83)
RT
ZF
.2,303lgim
(5.84)
i vi s phn cc catot: i = ic
ZF
c
RT
ic = im.exp
(5.85)
81
c =
RT
ZF
.2,303lgic
RT
ZF
.2,303lgim
(5.86)
E(v)NHE
+
1
0,00
H+ /H 2
Fe-2e
E cb
2+
Fe
-0,20
E m
2+
Fe /Fe
E cb
H+
i m
io
Fe
io
-5
-2
2H++2e
H2
2 lgi (A/cm2)
Hnh 5.10
ng phn cc (V) lgi (A/cm2)
1. H 2H+ + 2e
U H2 (pH = 0);
2. H Fe2+ + 2e
U Fe ( CFe2 + = 106M);
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:
m =
A.iam .t
ZF
(5.87)
82
m
S.t
dm2, m2) v t l thi gian din ra qu trnh n mn (gi, ngy m, thng, nm).
Ecb
Zn2 +
Ecb
2H+
Ecb
Fe
Zn
H2
= 0,441 +
= 0,76 +
0,059
2
0,059
2
lg 106 = 0,628 V
lg 106 = 0,937 V
= 0,00 V
H2
trn cc in cc Zn nh hn trn in cc st
83
E(V)
1
0,00
2H /H2
Ecb
Fe
-0,20
Em
1'
2'
-0,40
3
-0,60
Fe
Ecb
P'
3'
Zn
E m
-0,80
Zn
Ecb
-1,00
4'
lgi
Fe
lgio
Zn
lgio
-5
-2
Fe
lgim
Zn
(A/cm2)
Zn
lgi m p'
lgi m p
Hnh 5.11
ng phn cc E(V) - lgi(A/cm2)
4-4: H Zn2+ + 2e U Zn
( lg i )
Zn
am
2+
Fe
> lg iam
l v th EZn
cb
/ Zn
2+
< EFe
cb
/ Fe
Fe
v i Zn
o > io
Fe
Trong thc t i Zn
o.H2 < i o.H2 v th dng n mn ca km b gim i, ngha l:
( lg i )
Zn
am
P'
Zn
< lg i am
Me Ze Me2+
Phn ng anot:
Phn ng catot:
2H+ + Ze
Z
2
2
H2 E H
tn = 0,00 V
84
3+
v:
3+
/ Fe2+
= 0,77 V
2+
/ Fe
Do th ca h EFe
dng so vi h hiro cho nn kh nng nhn in t ca ion Fe3+
tn
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:
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 +
im O - th n mn Em nm gia Ecb
=|ia|.
Me
Ox
85
Ecb
Me
Ox
Eccb Eacb
(5.88)
( Ec < 0 )
(5.89)
( Ea > 0 )
(5.90)
i vi phn cc anot:
Eai = Eacb + Ea
(5.91)
c
Eci = Ecb
R Pc .i c
(5.92)
Eai = Eacb + R Pa .i a
(5.93)
ia = ic = im.
Khi pin n mn c tnh n s phn cc catot v anot th dng im c tnh theo cng
thc:
im =
Eci Eai
R
(5.94)
86
hoc
im =
hoc
Ta c:
im =
(5.95)
Eccb Eacb
(5.96)
R + RPc + R Pa
Rin
Rex
2
Rp
c
Rp
a
a
Ecb
E ia
c
Ei
c
Ecb
Hnh 5.13
S mch tng ng ca mt pin n mn gm hai in cc oxi ho kh n, trong :
Eccb Eacb
R Pc + RPa + R in + Rex
(5.97)
87
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)
Ea
Ea + Ec + iR
.100%
(5.98)
Ec
Ea + Ec + iR
.100%
(5.99)
iR
Ea + Ec + iR
.100%
(5.100)
89
Z
4
Z
4
O2 + Ze + ZH+
O2 + Ze +
Z
2
Z
2
H2O
H2O = ZOH
Nu kim loi st nhng trong mi trng axit cha oxi trong khng kh ho tan, s n
mn in ho xy ra:
Ti anot:
2Fe 4e 2Fe2+
(5.101)
Ti catot:
O2 + 4e + H2O 4OH
(5.102)
Ecb(O2 ) = Eo +
4F
ln
PO2
a4OH
(5.103)
2+
Cu 2e Cu
Trn catot xy ra phn ng:
1
2
O2 + 2e + H2O 2OH
90
v phn ng chung:
Cu +
1
2
trong : iOo 2
o
i O
2
CSO2
o
CO
2
4 c
exp O
2
RT
(5.104)
CSO2
o
CO
2
RT
ZF
sinh ra s phn cc nng , dng iC(O2 ) c tnh theo phng trnh Fick I v bng:
iC(O2 ) = 4FDO2
o
CO
CSO2
2
(5.105)
o
CO
2
(5.106)
hoc:
CSO2
o
CO
2
=1
=1
CSO2
(5.107)
o
CO
2
iC(O2 )
(5.108)
id
Kt hp (5.108) v (5.104) ta c:
iC(O2 ) = i o (1
iC(O2 )
id
O Fc
)exp 4 2
RT
(5.109)
91
iC(O2 )
O Fc
o
iO
exp 4 2
2
RT
=
o
iO
O Fc
1 2 exp 4 2
id
RT
(5.110)
id
RT
=
o
iO
O Fc
1 2 exp 4 2
id
RT
o
iO
2
iC(O2 )
id
o
iO
2
Nu s phn cc catot c rt nh v
id
(5.111)
rt nh th s hng
A =
O Fc
exp 4 2
ca (5.111) rt nh so vi 1 v khi phng trnh ng hc in ha
id
RT
o
iO
2
2
RT
RT
ZF
(5.112)
th s hng A rt ln so vi 1, t (5.111) ta
c:
iC(O2 ) = id
(5.113)
iC(O2 ) = id = 4FDO2
trong K l hng s.
o
CO
2
= K COo 2
(5.114)
92
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:
1.
2.
Lng
Lng
oxi
oxi
ha
ha
tan
tan
vi
nng
vi
nng
v
CO2 (2)
CO2 (1) ;
CO2 (1) .
z
2
(5.115)
93
M ze Mz+
(5.116)
Kim loi
Ho tan hot ng
Ho tan 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
95
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
96
(5.117)
(5.118)
(5.119)
(5.120)
S th ng ho t din bin - th ng ho ho hc
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
Em = ERedox > EP
(5.121)
(i )
(5.122)
ox
c
Cr
> iCr
98
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
2H2O + 4e + O2 4OH
Song ti vng giu oxi tc n mn ln, lng sn phm OH cng ln. Khi nng
OH tng, ti vng giu oxi d dng sinh ra trng thi th ng dn n s gim tc n
mn kim loi. Trong trng hp ny vng ngho oxi tc n mn kim loi li ln hn so
vi vng giu oxi (xem hnh 5.22).
99
lgi(A/m2)
ico2 (PO2,1)
lgi1m
lgi2m
ico2 (PO2,2)
Y1
D
C
lgi1'm
X1
A
Ep
X
2
EO2
E(V)
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
2
khi to th ng i2am > i1am .
Vi 2 1 > 2 2 ,i1am > iam
ng AQ - phn cc anot ng vi s ho tan kim loi vng hot ng ct ng XY ng cong phn cc catot ca in cc oxi c nng l 2 1 ln ti im P, khi sinh ra
dng n mn i1am ln. Tng t ti ch c nng oxi thp 2 2 , ng phn cc catot tiu
th oxi trong qu trnh n mn X1Y1 ct ng AQ ti N. Ti c dng n mn i2am nh.
Vy ti vng c p sut ho tan kh oxi cng ln th tc n mn kim loi (thp) cng ln.
Mt khc, ti im P c dng n mn, phn ng:
2H2O + 4e + O2 4OH
xy ra vi tc ln.
Kim ho vng b n mn v d dng gy ra hin tng th ng (i vi thp) v khi
dng n mn b gim t i1am i1'am . Trong iu kin ti ch c p sut 2 nh li c tc
n mn ln hn ti ch c p sut 2 ln, ngha l:
i2am > i1'
am
100
Me + Cl + H2O MeOHCl + H+ + 2e
(5.123)
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
Fe
Cr
Fe
hn l st (xem hnh 5.23) v iCr
v Cr
> iCr
p < p .
V vy ngi ta ch to hp kim st-crom FeCr hoc FeCrNi nhm mc ch nng cao
bn chng n mn ca thp. Nu thp c cha thnh phn Cr ln hn 12% c gi l thp
khng g, thp ny d dng i vo trng thi th ng khi tip xc vi nc c mt khng kh.
Hnh 5.23
ng phn cc anot c min th ng trong H2SO4 1N
1 - Kim loi crom; 2 - Kim loi st
101
Hnh 5.24
ng phn cc anot ca hp kim Fe13CrxMo trong dung dch HCl 1M
z
2
H2O ez / 2 + zH+ + ze
ez / 2 + zH+ + ze U Me +
z
2
H2O
(5.124)
hoc
Gi tr ooxit
oxit
Me
Me
= ooxit
= ooxit
Me
+ 0,059lg aH+
0,059pH
(5.125)
Me
ooxitCr
Cr
< ooxitNi
Ni
< ooxitFe
Fe
102
Dng oxit
Go (kJ/mol)
Eo (V)
Ti2O3 (hirat)
1388,0
1,169
Al2O3
1154,9
0,766
Ta2O5
1912,1
0,753
Cr2O3
1058,0
0,599
ZnO
318,3
0,420
MoO2
533,0
0,152
Fe3O4 (manhetit)
1016,5
0,087
Fe2O3 (hematit)
742,2
0,053
FeO
246,14
0,041
NiO
216,0
0,110
MoO3
688,0
0,075
183,7
0,277
CrO3
510,0
0,348
Pb3O4
616,2
0,431
Cu2O
148,1
0,462
CuO
319,0
0,535
103
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
Hin tng n mn kim loi do mi trng gy ra rt a dng v phc tp, c th tm
phn thnh cc loi sau y.
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:
Kim loi
Ni
Cu
Thp
cacbon
Al
99%
Zn
Mg
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
(6.1)
() Fe/H2SO4/(H2) Fe (+)
(6.2)
Zn
2
i vi pin (6.1) khi hot ng ta c dng im ca km bng: im
= iaZn = iH
c,Zn ng vi
Zn
th n mn Em
.
106
Tng t i vi pin (6.2), ti vng anot st b ha tan v cng gii phng hiro trn
H2
Fe
Fe
vng anot, vy ti EFe
m ta c i m = i a = i c,Fe .
Zn
ln
Khi so snh s hot ng ca hai pin (6.1) v (6.2) cho thy dng n mn ca Zn im
Fe
hn dng n mn ca st im , iu ny l do trong mi trng axit km hot ng hn st.
Fe
2
Nu ta gi thit dng iH
o,Zn = i o,Fe th dng n mn ca km cn ln hn so vi st rt
nhiu.
(6.3)
H2
+ Fe
Ni
Fe
2
iNi
= iH
m
c,Fe + i c,Ni = i m + i m
+ Fe
Ni
iNi
> iFe
m
m > i m
Hnh 6.3
Cc ng phn cc ca h n mn tip xc Ni+Fe trong dung dch H2SO4 long khng c oxi
107
(6.4)
Zn 2e Zn2+
Ti anot km b ho tan:
Zn +Pt
Zn
cb
E2H
> Em
> Em
> Ecb
+
Zn
/H
2
Zn + Pt
Zn
im
> im
Hnh 6.4
ng phn cc ca h n mn tip xc Zn-Pt trong mi trng axit H2SO4 long khng c oxi
108
Hnh 6.5a
ng phn cc ca h n mn tip xc Zn-Pt trong mi trng axit (din tch Pt tng ln)
109
(6.5)
3
1
1. in cc st;
4
4. Dung dch NaCl;
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
(6.6)
2
Dng n mn iFe
m2 vi p sut PO2 bng dng gii hn ca qu trnh catot tiu th oxi
id2 .
Fe
iFe
m2 = i d2 ng vi th n mn Em2 tnh theo im ct ca cc ng 1 v CC2.
111
(6.7)
hoc
+ H2O
FeOH+ + H2O
Fe
FeOH+ + H+ + 2e
v km theo phn ng ho hc
Fe(OH)2 + 2H+
(6.8)
112
K
T- Pha rn thp ;
K- Pha kh - khng kh ;
N- Pha lng - dung dch
nc bin ;
1- Vng b n mn ;
2- Lp g
Hnh 6.7
n mn mn nc
O2 + 2e + H2O 2OH
1
2
O2 + H2O Fe(OH)2
1
2
O2 + H2O 2Fe(OH)3
2Fe(OH)3 Fe2O3.3H2O
Fe(OH)2 + Fe2O3 Fe3O4.H2O
2Fe3O4 + 3H2O +
1
2
O2 3Fe2O3.3H2O
113
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
(6.9)
114
(6.10)
ng cong OABCDE - ng phn cc ho tan kim loi trong dung dch c cha
ion halogen X (Cl, Br, I).
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
(6.11)
115
Hnh 6.10
Dng n mn l ca thp th ng trong mi trng c mt Cl
116
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
117
6.5.1 n mn mi
Cc cu kin kim loi chu ti trng ng c th b gy do mt
ti trng nh hn ti
trng cc i m chng chu ng c trong
iu kin tnh. Hin tng gi l s
mi v dn n cc vt nt do mi.
Mi trng n mn lm tng tc giai on khi u v tc lan truyn cc vt nt do
s mi gy ra v t hp hai yu t li gi l s n mn mi.
Hin tng n mn mi cng rt phc tp, cho n nay vn cha c c ch r rng v
nh hng ca cc phn ng n mn i vi qu trnh mi.
Trong mt kt cu c th tn ti mt b phn c khuyt tt trn b mt do cc tp cht,
hoc cc vt nt do hn, g hoc l n mn v xem chng nh cc khe nt ban u, vy tui
th ca cu kin c quyt nh do tc lan truyn cc vt nt hoc cc khe khi c ti
trng. ng nhin s c mt ca mi trng n mn c nh hng ng k n tc lan
truyn.
trnh n mn mi c th s dng cc bin php sau: gim ti trng trn cc cu kin,
phun cc lp ht hoc nitrat ho b mt kim loi.
Mt khc cn phi loi tr bt cc tc nhn gy n mn ca mi trng, thay i th
bo v catot hoc sn ph.
6.5.1 n mn chn lc
118
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.
119
P
Po
.100%
(6.12)
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.
b) nh hng ca cht nhim bn
Hnh 6.11
Tn tht trng lng (g/m2) ca thp cacbon theo thi gian (ngy)
120
Me ze Mez+
z
2
O2 + ze + zH2O 2zOH
trong : P l tc n mn;
a, b l cc h s;
t l thi gian nm.
121
122
123
Hnh 6.12
S n mn ct thp btng
Ti anot:
Tai catot:
Fe 2e Fe2+
1
2
O2 + 2e + H2O 2OH
6.5.6 n mn vi sinh
124
+ 4O
125
Chng 7
S n mn vt liu kim loi v cc bin php bo v
kim loi chng n mn in ha
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.
1
4
O2 +
3
2
H2O 3FeOOH
126
2H2O + 2e H2 + 2OH
Thng phn ng din ra rt chm, nhng khi tng nhit tc n mn tng ln. i
vi phn ng kh oxi, tc phn ng ph thuc vo nng oxi ho tan trong nc. Nu
hm lng mui cao th tc ho tan oxi gim.
Trong nc bin tnh tc n mn c tn theo cng thc:
P( mm
nm
=K
CO2
(7.1)
1
2
O2 + 2e H2O
127
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.
128
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
t khc
Loi
%Cmax
%Cr
210
0,15
16 18
304
0,08
18 20
8 12
1
(Max)
Si
304L
0,03
18 20
8 12
1
(Max)
Si
316
0,10
16 18
316L
0,03
16 18
322
0,07
17
410
0,15
430
0,12
14 18
431
0,2
15 17
11,5
%Ni
3,5
5,5
10
10
14
14
13,5
2 3 Mo
2 3 Mo
0,07
0,2 Al
0,5
(Max)
1,25
2,5
5 7 Mn
Ti,
Thp ny cha hm lng Cr khong 13% 17% v nhiu cacbon hn thp ferit. Nhiu
thp Mactensit c lng Cr thp hn 11% (thc ra khng phi l thp khng g). Loi thp
Mactensit 11,5 13,5% Cr c th bn cng, n l loi st t kh hn, kh nng chng n mn
cao.
Thp ny c s dng lm trc bm, pittng, van ca h thng thu lc, cc chi tit ca
tuc-bin hi.
Thp khng g Ostenit
Khi thm Ni vo thp khng g Cr s m rng vng Ostenit v ci thin c tnh ca thp.
Loi ny c thnh phn: 16 25% Cr v 8 20% Ni, C < 0,08%; nu c mt Mo th kh nng
th ng ca thp tng ln.
Thp ny c do cao, d hn, bn chng n mn trong HNO3 thp hn 65% nhit
thng v khng bn trong HNO3 c nhit cao.
129
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:
Cu2+
Mi trng
1M
Gi tr in th
E(V)
NaCl
3%
0,34
HCl
1N
0,06
0,15
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
o
th EoRe d > ECu2
= 0,34 V . Nu c mt cc ion hoc hp cht Cl , NH3, CN , khi th
+
Cu
o
cn bng ca ng ECu
2+
cht phc.
V d: Cu trong dung dch Cl 25oC xy ra phn ng:
Cu + 2Cl CuCl2 + 1e
hoc
CuCl2 + 1e U Cu + 2Cl
v th in cc:
vi
Cu
th
= 1,94 + 0,059 lg
cb
ECuCl
= 0,160 V
cb
ECuCl
Cu
aCuCl
2
2
aCl
130
Khi thm cc nguyn t hp kim nh Sn, Zn, Al, Ni, Be vo ng th tnh cht c hc ca
ng tng ln mt cch ng k.
Cc loi hp kim Cu-Zn v Cu-Sn thuc loi hp kim c bn c hc v bn chng
n mn rt cao (gi l kim loi kin trc c nht xp x 4000 nm).
ng thau Cu-Zn (30% Zn) c s dng rng ri trong vic ch to cc thit b trao i
nhit v ngng t cho cc thit b nh: t, t lnh Nu thm vo hp kim mt lng nh
As (0,02 0,06% As) s nng cao bn chng n mn vt liu v loi tr c hin tng
n mn chn lc km. C th dng vt liu Cu-Zn 30% hoc Cu-Zn29Sn1 (c th c As) lm
thit b ngng t hoc thit b lnh cng nghip vi nc c mt ion Cl.
Khi s dng nc bin lm lnh th dng vt liu Cu-Zn22Al2 (ng thau nhm)
ch to cc ng ng.
Trong mt s trng hp cc thit b truyn nhit hoc lm lnh c yu cu cao hn v
bn chng mi mn, n mn th ngi ta s dng cc hp kim Cu-Ni. V d Cu-Ni 10, CuNi 30. Tnh bn c th tng thm nu thm vo hp kim trn mt lng 0,5 1,5% Fe (gi l
Cunifer), s c mt ca st lm tng bn lp bo v khi tc dng chy cao.
Trong trng hp nc bin c nhiu cht nhim lm tng kh nng mi mn v n
mn, cc vt liu Cu, thp khng g khng p ng v bn th ngi ta dng Ti hoc hp
kim Ti.
131
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.
132
Phn ng anot:
Phn ng catot:
3H2O + 3e U
H2 + 3OH
Al + 3H2O + OH U [Al(OH)4] +
3
2
H2
Trong cc axit HNO3, H3PO4 v H2SO4 long Al khng b n mn. Trong cc axit HCl,
HF, H2SO4 Al b ho tan. Nu trong dung dch cha cc ion Hg2+, Al b ho tan nhanh to ra
hn hng. Nhm nguyn cht c bn c hc km, v vy dng hp kim nhm song bn
chng n mn ca cc hp kim li km so vi nhm nguyn cht. C th cn ln b mt hp
kim nhm mt lp nhm nguyn cht tng bn chng n mn.
Hp kim nhm
Th
t
K hiu hp kim
H hp kim
Tiu
(TCVN)
chun
VN
Tiu
chun AA
Thnh
phn %
(*)
1
2
Al sch
Loi
nghip
cng
Al 99,6
1060
99,6
Al 99,0
1100
99,0 Al
Al-Cu-Mg
AlCu4,4Mg1,5Mn0,6
2024
4,4Cu1,5Mg-0,6Mn
Al-Mn
AlMn1,2
3004
1,2Mn0,12Cu
Al-Mg-Si
AlMg1Si0,6
6061
1Mg0,6Si-0,2Cr-
133
0,3Cu
Al-Zn-Mg
Al-Cu 4,5
AlZn4,5Mg1,4
7005
2950
4,5Zn1,4Mg-0,12Cr
-0,4Mn1,5Zr
4,5Cu-1Si
134
a) Phng php ha hc
N2H4 + O2 2H2O + N2
(7.2)
135
(7.3)
lgi Cr
2
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
S dng cc kim loi c nhit nng chy thp Zn (419oC), Sn (232oC), Pb (327oC), Al
(658oC) ph ln cc vt liu kim loi cn bo v c nhit nng chy cao. V d ph km
nng chy ln nn thp.
137
ZnSO4.7H2O
Na2SO4.10H2O
50 100 g/l
Al2(SO4)3.18H2O
20 30 g/l
Ph gia extrin 10 g/l. Nhit 25oC 30oC, pH = 3,5 4,5. Mt dng catot DC = 1
4 A/dm2. Anot - kim loi km.
B m ny ch dng m cc chi tit n gin. i vi nhng chi tit phc tp ngi ta s
dng dung dch phc c thnh phn sau (theo g/l):
:
10 18;
NaCN :
20 30
NaOH :
50 70;
Na2S :
0,5 5
ZnO
12 15;
NH4Cl :
240 260
138
H3BO3 :
20 25;
gelatin :
12
H2SO4 :
Na2Cr2O7 :
50 70 g/l,
H2SO4 :
139
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
2H+ + 2e H2
ZZZZZZZ
X
Mn(H2PO4)2 YZZZZZZ
Z MnHPO4 + H3PO4
3MnHPO4
nc nng
ZZZZZZZ
X
YZZZZZZ
Z Mn3(PO4)3 + H3PO4
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
O2HOH
Ant
Al3+
1
O22
141
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).
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.
143
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
144
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.
145
Hnh 7.5
S bo v chng n mn kim loi bng anot hy sinh
Hp
kim
AlZn-Mg
Mi
trng
Nc
bin
in th lm vic
Dung lng
(so vi in cc bc trong
Ah/kg
nc bin)
1,0 1,05
2600 2850
AlZn-In
-nt-
1,0 1,10
2300 2650
AlZn-Sn
-nt-
1,0 1,05
925 2600
Zn
-nt-
0,95 1,03
760 780
-nt-
1,05
780
ZnAl-Cd
146
MgAl-Zn
MgMn
-nt-
1,50
1230
-nt-
1,7
1230
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
Cc phng php xc nh tc n mn kim loi
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
C bn trung bnh
bn thp
bn rt thp
Hon ton khng bn
bn
Xp loi
0,001
0,001 0,005
0,005 0,01
0,01 0,05
0,05 0,1
0,1 0,5
0,5 1,0
1,0 5,0
5,0 10,0
> 10,0
10
148
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.
mo m1
S.t
S.t
(8.1)
trong : - tc n mn;
mo - trng lng mu kim loi trc khi th nghim (g) hoc (mg);
m1 - trng lng mu kim loi sau th nghim (g) hoc (mg);
S - din tch b mt kim loi;
t - thi gian (gi) hoc (ngy, m) hoc nm.
Nu m (mg), S (dm2) v t (ngy m) ta c:
[] = mg/dm2.ngy m
(8.2)
(8.3)
149
n v o:
[P] = l/t
(8.4)
.0,0365
mm/nm
(8.5)
Nu chn [P] = mm/nm, [] = g/m2.h, [d] = g/cm3 th quan h gia chng bng:
= 8,76.
mm/nm
(8.6)
150
5
1
Ea
2
thi gian (t)
Hnh 8.1
Hnh 8.2.
1 - in cc lm vic (WE)
2 - in cc so snh (RE) - in cc bc
7
3 - Von k c R ln hn 10
151
7
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
i (A/cm )
1
2
E (V)
+
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+
ng Tafel ant
e+
M
ze
Em
zH +
ng Tafel catt
+z
e
z
2 H
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)
S o ng cong phn cc theo phng php th tnh c trnh by trn hnh (8.6).
153
Potentiostat
WE
RE
CE
Hnh 8.6
S o ng phn cc theo phng php th
tnh
1. in cc lm vic (WE); 2. in cc so snh
(RE); 3. in cc ph tr (CE); 4. Dung dch
cht in li; 5,6. Ccmilivol k;7. Potentiostat;
8. in tr mu c gi tr bit trc
(8.7)
z
2
H2
(8.8)
154
d ( E )
Rp =
di
=
m
(8.9
im
E (V)
Me - ze
Me z+
E m
z H
2
2
zH + + ze
Hnh 8.7
ng cong phn cc E - f(i)
b .be
2,3. ( b + be )
(8.10)
Rp
(8.11)
(8.12)
155
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
Bng gi tr th tiu chun ca cc phn ng in ho trong dung dch nc so vi in
cc tiu chun (NHE)
STT
Phn ng in cc
Eo(V)
Li+ + e = Li
3,024
Cs+ + e = Cs
3,020
Ca(OH)2 + 2e = Ca + 2OH
3,020
Rb+ + e = Rb
2,990
2,990
2,097
2,930
K+ + e = K
2,924
Ra2+ + 2e = Ra
2,920
10
Ba2+ + 2e = Ba
2,900
11
Sr2+ + 2e = Sr
2,890
12
Ca2+ + 2e = Ca
2,870
13
La(OH)3 + 3e = La + 3OH
2,800
14
Lu(OH)3 + 3e = Lu + 3OH
2,720
15
Na+ + e = Na
2,714
16
Mg(OH)2 + 2e = Mg + 2OH
2,680
17
2,640
18
Sc(OH)3 + 3e = Sc + 3OH
2,600
19
2,500
20
Ce3+ + 3e = Ce
2,480
157
STT
Phn ng in cc
Eo(V)
21
Nd3+ + 3e = Nd
2,440
22
Pu(OH)3 + 3e = Pu + 3OH
2,420
23
Sm3+ + 3e = Sm
2,410
24
Gd3+ + 3e = Gd
2,400
25
UO2 + 2H2O + 4e = U + OH
2,390
26
La3+ + 3e = La
2,370
27
Y3+ + 3e = Y
2,370
28
2,350
29
Mg2+ + 2e = Mg
2,340
30
2,320
31
Am3+ + 3e = Am
2,320
32
Al(OH)3 + 3e = Al + 3OH
2,310
33
2,28
34
Lu3+ + 3e = Lu
2,25
2,23
35
H2 + e = H
36
U(OH)4 + e = U(OH)3 + OH
2,20
37
U(OH)3 + 3e = U + 3OH
2,17
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
STT
Phn ng in cc
Eo(V)
43
Np3+ + 3e = Np
1,86
44
H2PO2 + e = P + 2OH
1,82
45
U3+ + 3e = U
1,80
46
1,80
47
1,79
48
Ti2+ + 2e = Ti
1,75
49
1,73
50
1,71
51
Hf4+ + 4e = Hf
1,70
52
Be2+ + 2e = Be
1,70
53
1,68
54
Al3+ + 3e = Al
1,67
55
1,65
56
1,61
57
Zr4+ + 4e = Zr
1,53
58
[Fe(CN)6]4 + 2e = Fe + 6CN
1,50
59
Mn(OH)2 + 2e = Mn + 2OH
1,47
60
ZnS + 2e = Zn + S2
1,44
61
1,43
62
1,40
63
1,40
64
1,37
159
STT
Phn ng in cc
Eo(V)
65
MnCO3 + 2e = Mn + CO32
1,35
66
Cr(OH)3 + 3e = Cr + 3OH
1,30
67
1,28
68
[Zn(CN)4]2 + 2e = Zn + 4CN
1,26
69
Zn(OH)2 + 2e = Zn + 2OH
1,245
70
CdS + 2e = Cd + S2
1,23
71
72
73
74
SiF62 + 4e = Si + 6F
75
1,22
1,216
1,20
1,20
TiF62 + 4e = Ti + 6F
1,19
76
1,18
77
V2+ + 2e = V
1,18
78
3
16H2O + HV6O17
+ 30e = 6V + 33OH
1,15
79
1,15
80
1,14
81
Nb3+ + 3e = Nb
1,10
82
NiS ( ) + 2e = Ni + S2
1,07
83
ZnCO3 + 2e = Zn + CO32
1,06
84
BF4 + 3e = B + 4F
1,06
85
Mn2+ + 2e = Mn
1,05
86
1,05
160
STT
Phn ng in cc
Eo(V)
87
1,05
88
1,05
89
1,05
90
Tl2S + 2e = 2Tl + S2
1,04
91
1,03
92
FeS() + 2e = Fe + S2
1,01
93
In(OH)3 + 3e = In + 3OH
1,0
94
PbS + 2e = Pb + S2
0,98
95
0,96
96
0,96
97
Pu(OH)4 + e = Pu(OH)3 + OH
0,95
98
0,95
99
Cu2S + 2e = 2Cu + S2
0,95
100
0,95
101
SnS + 2e = Zn + S2
0,94
102
CoS() + 2e = Co + S2
0,93
103
Te + 2e = Te2
0,92
104
Cd ( CN )4 + 2e = Cd + 4CN
105
0,90
106
Cr2+ + 2e = Cr
0,90
107
0,88
108
0,88
0,90
161
STT
Phn ng in cc
Eo(V)
109
Fe(OH)2 + 2e = Fe + 2OH
0,877
110
NiS() + 2e = Ni + S2
0,86
111
SbS2 + 3e = Sb + 2S
112
0,85
113
0,84
114
[Co(CN)6]3 + e = [Co(CN)6]4
0,83
115
PtS + 2e = Pt + S2
0,83
116
2H2O + 2e = H2 + 2OH
0,828
117
UO22+ + 4H + 6e = U + H2O
0,82
118
[Ni(CN)4]2 + e = [Ni(CN)3]2 + CN
0,82
119
Cd(OH)2 + 2e = Cd + 2OH
0,81
120
0,81
121
CdCO3 + 2e = Cd + CO32
0,80
122
0,799
123
0,79
124
Se + 2e = Se2
0,78
125
Zn2+ + 2e = Zn
0,762
126
TlI + e = Tl + I
0,76
127
CuS + 2e = Cu + S2
0,76
128
FeCO3 + 2e = Fe + CO32
0,755
129
AsS2
130
CrCl2+ + 3e = Cr + 2Cl
0,85
+ 3e = As + 2S2
0,75
0,74
162
STT
Phn ng in cc
Eo(V)
131
Co(OH)2 + 2e = Co + 2OH
0,73
132
0,73
133
0,73
134
Cr3+ + 3e = Cr
0,71
135
Ag2S + 2e = 2Ag + S2
0,71
136
0,71
137
HgS + 2e = Hg + S2
0,70
138
0,70
139
Te + 2H+ + 2e = H2Te
0,70
140
Ni(OH)2 + 2e = Ni + 2OH
0,69
141
0,68
142
0,67
143
Fe2S3 + 2e = 2FeS + S2
0,67
144
0,66
145
TlBr + e = Tl + Br
0,658
146
Ga3+ + e = Ga2+
0,65
147
CoCO3 + 2e = Co + CO32
0,632
148
0,63
149
U4+ + e = U3+
0,61
150
SO24 + 3H2O + 6e = S
151
Au ( CN )2 + e = Au + 2CN
0,60
152
AsS34 + 2e = AsS2 + 2S
0,60
+ 6OH
0,61
163
STT
Phn ng in cc
Eo(V)
153
[Cd(NH3)4]2+ + 2e = Cd + 4NH3(A)
0,597
154
0,594
155
0,59
156
0,59
157
Re O4 + 4H2O + 7e = Re + 8OH
0,584
158
NO3 + NO + e = 2NO2
0,58
159
0,58
160
CuS + 2e = Cu2S + S2
0,58
161
0,578
162
0,576
163
0,57
164
Fe(OH)3 + e = Fe(OH)2 + OH
0,56
165
PbS + H2O + 2e = Pb + OH + SH
0,56
166
O2 + e = O2
0,56
167
TlCl + e = Tl + Cl
0,577
168
2NH4+ + 2e = 2NH3(A) + H2
0,55
169
S + S3 + 2e = S24
0,55
170
As + 3H+ + 3e = Pb + 3OH
0,54
171
0,54
172
Cu2S + 2e = 2Cu + S2
0,54
173
Ga3+ + 3e = Ga
0,520
164
Eo(V)
STT
Phn ng in cc
174
S22 + 2e = 2S
0,510
175
[Ag(CN)3]2 + e = Ag + 3CN
0,51
176
Sb + 3H+ + 3e = SbH3
0,577
177
H3PO2 + H+ + e = P + 2H2O
0,510
178
S + 2e = S2
0,508
179
PbCO3 + 2e = Pb + CO32
0,506
180
0,50
181
0,49
182
0,49
183
0,48
184
0,46
185
0,46
186
0,45
187
NiCO3 + 2e = Ni + CO32
045
188
In3+ + e = In2+
0,45
189
Fe2+ + 2e = Fe
0,441
190
191
Eu3+ + e = Eu2+
0,43
192
[Cu(CN)2] + e = Cu + 2CN
0,43
193
0,422
194
2H+ + 2e = H2 (pH 7)
0,414
H2O
0,435
165
STT
Phn ng in cc
Eo(V)
195
Cr3+ + e = Cr2+
0,41
196
Cd2+ + 2e = Cd
0,402
197
Mn(OH)3 + e = Mn(OH)2 + OH
0,40
198
0,40
199
Hg ( CN )4 + 2e = Hg + 4CN
0,37
200
Ti3+ + e = Ti2+
0,37
201
0,366
202
PbI2 + 2e = Pb + 2I
0,365
203
0,361
204
Se + 2H+ + 2e = H2Se
0,36
205
0,36
206
0,36
207
In2+ + e = In+
0,35
208
Tl(OH) + e = Tl + OH
0,344
209
In3+ + 3e = In
0,340
210
InCl + e = In + Cl
0,34
211
Tl+ + e = Tl
0,338
212
0,30
213
[Ag(CN)2] + e = Ag + 2CN
0,361
214
0,30
215
PbBr2 + 2e = Pb + 2Br
0,280
216
Co2+ + 2e = Co
0,277
217
0,276
166
Eo(V)
STT
Phn ng in cc
218
HCNO + H+ + e =
219
Cu(CNS) + e = Cu + CNS
0,27
220
PbCl2 + 2e = Pb + 2Cl
0,268
221
0,259
222
V3+ + e = V2+
0,255
223
0,255
224
V ( OH )4 + 4H + 5e = V + 4H2O
0,253
225
Ni2+ + 2e = Ni
0,250
226
SnF62 + 4e = Sn + 6F
0,25
227
0,25
228
0,24
229
0,23
230
N2 + 5H+ + 4e = N2H5+
0,23
231
Cu(OH)2 + 2e = Cu + 2OH
0,23
232
0,224
233
Mo3+ + 3e = Mo
0,2
234
CuI + e = Cu + I
0,187
235
0,180
236
0,16
237
AgI + e = Ag + I
0,151
238
0,15
1
2
0,27
(CN)2 + H2O
167
STT
Phn ng in cc
Eo(V)
239
Sn2+ + 2e = Sn
0,140
240
0,14
241
0,13
242
Pb2+ + 2e = Pb
0,126
243
0,12
244
[Cu(NH3)2]+ + e = Cu + 2NH3
0,11
245
0,09
246
0,09
247
O2 + H2O + 2e = HO2 + OH
0,076
248
0,05
249
0,05
250
0,05
251
0,05
252
Hg2I2 + 2e = 2Hg + 2I
0,0405
253
HgI24 + 2e = Hg + 4I
0,04
254
Ti4+ + e = Ti3+
0,04
255
P + 3H+ + 3e = PH3
0,04
256
AgCN + e = Ag + CN
0,04
257
0,04
258
Fe3+ + 3e = Fe
0,036
259
0,036
260
0,02
168
STT
Phn ng in cc
Eo(V)
261
0,01
262
2D+ + 2e = D2
0,0034
263
0,0
264
CuI2 + 2e = Cu + 2I
0,0
265
0,0000
266
2H+ + 2e = H2
0,0000
267
[Ag(S2O3)2]3 + e = Ag + 2S2O32
0,01
268
269
0,02
270
0,02
271
0,03
272
CuBr + e = Cu + Br
0,033
273
0,04
274
UO22+ + e = UO2+
0,05
275
CuBr2 + e = Cu + 2Br
0,05
276
CuCO3 + 2e = Cu + CO32
0,053
277
P + 3H+ + 3e = PH3
0,06
278
0,07
279
Pd(OH)2 + 2e = Pd + 2OH
0,07
280
AgBr + e = Ag + Br
0,073
281
AgNCS + e = Ag + NCS
0,09
282
0,098
0,01
169
STT
Phn ng in cc
Eo(V)
283
Si + 4H+ + 4 e = SiH4
0,102
284
Pd(OH)2 + 2e = Pd + 2OH
0,1
285
0,1
286
0,1
287
[Co(NH3)6]3+ + e = [Co(NH3)6]2+
0,1
288
2NO + 2e = N2O22
0,1
289
0,1
290
Mn(OH)3 + e = Mn(OH)2 + OH
0,1
291
0,123
292
CuCl + e = Cu + Cl
0,124
293
C + 4H+ + 4e = CH4
0,13
294
0,139
295
S + 2H+ + 2e = H2S
0,141
296
Np4+ + e = Np3+
0,147
297
Sn4+ + 2e = Sn2+
0,15
298
Re O4 + 8H + 7e = Re + H2O
0,15
299
0,15
300
0,152
301
BiCl4 + 3e = Bi + 4Cl
0,16
302
Pt(OH)2 + 2e = Pt + OH
0,16
303
0,16
304
Cu2+ + e = Cu+
0,167
305
S4 O62 + 2e = 2S2O32
0,17
170
Eo(V)
STT
Phn ng in cc
306
307
CuCl2 + e = Cu + 2Cl
0,19
308
0,194
309
0,20
310
S2O62 + 4H + 2e = 2H2SO3
0,20
311
0,20
312
Co(OH)3 + e = Co(OH)2 + OH
0,20
313
HgBr42 + 2e = Hg + 4Br
0,21
314
SbO+ + H+ + 3e = Sb + H2O
0,212
315
AgCl + e = Ag + Cl
0,222
316
0,22
317
0,23
318
0,24
319
0,24
320
0,244
321
0,247
322
0,25
323
0,25
324
0,252
325
IO5 + 3H2O + 6e = I
326
PuO2(OH)2 + e = PuO2OH + OH
0,26
327
0,267
+ 6OH
0,17
0,26
171
STT
Phn ng in cc
Eo(V)
328
0,283
329
[Ag(SO3)2]3 + e = Ag + 2SO32
0,230
330
0,314
331
0,32
332
0,32
333
UO32+ + 2 e = UO2
0,33
334
033
335
UO22+ + 4H + 2e = U
0,334
336
0,336
337
0,344
338
Cu2+ + 2e = Cu
0,345
339
340
Fe ( CN )6 + e = Fe ( CN )6
0,36
341
0,36
342
AgIO3 + e = Ag + IO3
0,37
343
Ti3+ = Ti4+ + e
0,37
344
0,373
345
HgCl24 + 2e = Hg + 4Cl
0,38
346
Hg(IO3)2 + 2e = Hg + 2IO3
0,40
347
0,40
348
U6+ + 2e = U4+
0,4
349
4+
+ 2H2O
0,35
0,4
172
Eo(V)
STT
Phn ng in cc
350
O2 + H2O + e = OH
351
FeF63 + e = Fe
352
O2 + H2O + 4e = 4OH
0,401
353
0,417
354
0,42
355
0,44
356
RhCl36 + 3e = Rh + 6Cl
0,44
357
0,446
358
0,45
359
0,45
360
0,47
361
0,47
362
0,48
363
0,48
364
PdI62 + 2e = PdI24 + 2I
365
0,49
366
0,49
367
IO + H2O + 2e = I + 2OH
0,49
368
AuI + e = Au + I
0,50
369
0,5
370
Re O4 + 4H + 3e = ReO2 + 2H2O
0,51
371
ClO4 + 4H2O + 8e = Cl
2+
+ HO2
0,4
+ 6F
0,4
0,48
+ 8OH
0,51
173
STT
Phn ng in cc
Eo(V)
372
0,52
373
0,52
374
Cu+ + e = Cu
0,522
375
0,529
376
0,53
377
I2 + 2e = 2I
0,534
378
I3 + 2e = 3I
379
0,54
380
MnO4 + e = MnO24
0,54
381
0,54
382
AgBrO3 + e = Ag + BrO3
0,55
383
0,559
384
0,559
385
0,56
386
Cu2+ + Cl + e = CuCl
0,56
387
AgNO2 + e = Ag + NO2
0,564
388
Te4+ + 4e = Te
0,568
389
0,57
390
0,57
391
0,58
392
393
PtBr42 + 2e = Pt + 4Br
0,535
0,58
0,58
174
STT
Phn ng in cc
Eo(V)
394
0,581
395
396
OsCl36 + 3e = Os + 6Cl
397
PdBr42 + 2e = Pd + 4Br
398
0,59
0,60
0,60
RuCl52 + 3e = Ru + 5Cl
0,60
399
RuO4 + e = RuO24
0,60
400
0,60
401
0,61
402
0,615
403
0,62
404
0,62
405
UO22+ + 4H + 2e = U
0,62
406
0,63
407
0,63
408
PdCl24 + 2e = Pd + 4Cl
0,64
409
AgC2H3O2 + e = Ag + CH3COO
0,643
410
0,645
411
0,653
412
Cu2+ + Br + e = CuBr
0,657
413
0,66
414
Au ( NCS )4 + 3e = Au + 4NCS
4+
+ 2H2O
0,66
175
Eo(V)
STT
Phn ng in cc
415
0,66
416
AgBrO3 + e = Ag + BrO3
0,68
417
0,68
418
0,68
419
O2 + 2H+ + 2e = H2O2
0,682
420
Cu2+ + 2I + e = CuI2
0,690
421
Au ( NCS )2 + e = Au + 2NCS
0,69
422
0,699
423
H3 IO42 + 2e = IO
424
Te + 2H+ + 2e = H2Te
0,70
425
0,70
426
0,72
427
IrCl36 + 3e = Ir + 6Cl
428
PtCl24 + 2e = Pt + 4Cl
0,73
429
[Mo(CN)6]3 + e = [Mo(CN)6]4
0,73
430
0,74
431
0,74
432
0,74
433
0,75
434
NpO2+ + 4H + e = Np
0,75
435
0,76
436
(NCS)2 + 2e = 2NCS
0,77
+ 3OH
0,70
0,72
4+
+ 2H2O
176
STT
Phn ng in cc
Eo(V)
437
Fe3+ + e = Fe2+
0,771
438
Hg 22+ + 2e = 2Hg
0,789
439
0,79
440
Ag+ + e = Ag
0,7991
441
0,80
442
0,80
443
Rh3+ + 3e = Rh
~ 0,8
444
0,82
445
0,85
446
0,86
447
Cu2+ + I + e = CuI
0,86
448
0,86
449
AuBr4 + 3e = Au + 4Br
450
2IBr2 + 2e = I2 + 4Br
451
0,88
452
N2O4 + 2e = 2NO2
0,88
453
0,89
454
0,9
455
0,9
456
2Hg2+ + 2e = Hg 22+
0,920
457
PuO22+ + e = PuO2+
0,73
458
0,94
0,87
0,87
177
STT
Phn ng in cc
Eo(V)
459
NO3 + 4H + 3e = NO + 2H2O
0,96
460
461
AuBr2 + e = Au + 2Br
0,96
462
Pu4+ + e = Pu3+
0,97
463
0,98
464
Pd2+ + 2e = Pd
0,987
465
HIO3 + H+ + 2e = I + H2O
0,99
466
IrBr63 + e = IrBr64
0,99
467
0,99
468
HNO2 + H+ + e = NO + H2O
1,00
469
1,00
470
AuCl4 + 3e = Au + 4Cl
471
+
2+
V ( OH )4 + 2H + e = VO + 3H2O
1,00
472
IrCl62 + e = IrCl36
1,017
473
1,02
474
2IBr + 2e = I2 + 2Br
1,02
475
1,03
476
VO34+ + 6H + e = VO
1,031
477
PuO22+ + 4H + 2e = Pu
478
2ICl3 + 6e = I2 + 6Cl
479
ICl2 + e = 2Cl
1,00
2+
+ 3H2O
4+
1
2
0,96
+ 2H2O
1,04
1,05
I2
1,06
178
STT
Phn ng in cc
Eo(V)
480
1,06
481
Br2 + 2e = 2Br
1,0652
482
1,07
483
IO3 + 6H + 6e = I
484
485
486
AuCl2 + e = Au + 2Cl
487
PuO2+ + 4H + e = Pu
488
1,15
489
NpO22+ + e = NpO2+
1,15
490
ClO2 + e = ClO2
1,16
491
CCl4 + 4e = 4Cl + C
1,18
492
1,19
493
2ICl + 2e = I2 + 2Cl
1,19
494
IO3 + 6H + 5e =
495
BrCl + 2e = Br + Cl
1,20
496
Pt2+ + 2e = Pt
~1,2
497
1,2
498
1,21
499
O2 + 4H+ + 4e = 2H2O
1,229
500
+ 3H2O
4+
+ 2H2O
1
2
I2 + 3H2O
1,1
1,12
1,13
1,085
1,15
1,195
1,23
179
STT
Phn ng in cc
Eo(V)
501
S2Cl2 + 2e = 2S + 2Cl
1,23
502
1,23
503
O2 + H2O + 2e = O2 + 2OH
1,24
504
Tl3+ + 2e = Tl+
1,25
505
AmO2+ + 4H + e = Am
506
N2H4 + 4H + 2e = 2NH4+
+
1,275
507
ClO2 + H+ + e = HClO2
1,275
508
1,288
509
1,29
510
Au3+ + 2e = Au+
~1,29
511
HBrO + H+ + 2e = Br + H2O
1,33
512
1,33
513
CrO4 + 8H + 7e =
Cr2 + 4H2O
1,34
514
1,35
515
Cl2 + 2e = 2Cl
1,3595
516
Tl3+ + Cl + 2e = TlCl
1,36
517
IO4 + 8H + 8e = I
518
1,4
519
1,42
520
BrO3 + 6H + 6e = Br
521
522
ClO3 + 6H + 6e = Cl
4+
+ 2H2O
3+
1
2
+ 4H2O
+ 7H2O
+ 3H2O
+ 3H2O
1,26
1,4
1,44
1,45
1,45
180
Eo(V)
STT
Phn ng in cc
523
HIO + H+ + e =
524
525
ClO3 + 6H + 5e =
526
HClO + H+ + 2e = Cl + H2O
1,49
527
Au3+ + 3e = Au
1,50
528
1,50
529
HO2 + H+ + e = H2O2
1,50
530
Mn3+ + e = Mn2+
1,51
531
MnO4 + 8H + 5e = Mn
532
BrO3 + 6H + 5e =
533
534
HBrO + H+ + e =
535
1,59
536
1,59
537
1,6
538
Bk4+ + e = Bk3+
1,6
539
Ce4+ + e = Ce3+
1,61
540
1,63
541
AmO22+ + e = AmO2+
1,64
542
1,64
543
1,68
1
2
I2 + H2O
1
2
Cl2 + 3H2O
2+
1
2
1
2
1,45
1,455
1,47
+ 4H2O
1,51
Br2 + 3H2O
1,52
Br2 + H2O
1,56
1,59
181
STT
Phn ng in cc
Eo(V)
544
1,685
545
AmO22+ + 4H + 3e = Am
1,69
546
Pb4+ + 2e = Pb2+
1,69
547
1,695
548
AmO2+ + 4H + 2e = Am
1,725
549
1,77
550
Co3+ + e = Co2+
1,82
551
FeO24 + 8H + 3e = Fe
552
1,96
553
Ag2+ + e = Ag+
1,98
554
OH + e = OH
2,0
555
S2O82 + 2e = 2SO24
2,01
556
O3 + 2H+ + 2e = O2 + H2O
2,07
557
2,1
558
Am4+ + e = Am3+
2,18
559
O + 2H+ + 2e = H2O
2,42
560
F2 + 2e = 2F
2,65
561
OH + H+ + e = H2O
2,8
562
2,85
563
F2 + 2H+ + 2e = 2HF
3,06
3+
3+
3+
+ 2H2O
+ 2H2O
+ 4H2O
1,9
182
K hiu
, fN,fC
H s Vanhof
dn in ring
Hng s kh l tng
in tr sut
Nhit Kenvin
S Faraday
Hng s in li
in dung lp kp
in tch ion
Hng s in mi lp kp
NA
S Avogaro
Cng dng in
Hiu ng nhit ca i
phn ng
,
Mt dng in
Bin thin th ng t
nhit ng p
t+
S ti
S ti anion
Nng mol/l
Linh cation
Nng molan
Linh anion
Ha th
Th in cc
Sc in ng
H s chuyn in
S ti cation
183
1.
2.
3.
4.
5.
6.
7.