1

n mn v bo v kim loi
Trnh Xun Sn

NXB i hc quc gia H Ni 2006.

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.

Ti liu trong Th vin in t H Khoa hc T nhin c th c s dng cho mc
ch hc tp v nghin cu c nhn. Nghim cm mi hnh thc sao chp, in n phc
v cc mc ch khc nu khng c s chp thun ca nh xut bn v tc gi.

Mc lc
Chng 1 Phn m u ......................................................................................................... 5
1.1

nh ngha v s n mn kim loi ............................................................................. 5

1.2

Tm quan trng v mt kinh t ca vn n mn kim loi ..................................... 6

1.3

Nhng khi nim c bn ............................................................................................ 7

1.3.1

Cc phn ng n mn kim loi............................................................................... 7

1.3.2

nh lut Faraday ................................................................................................... 8

1.3.3

Pin in ha v bnh in phn .............................................................................. 8

Chng 2 S n in ca dung dch cht in li............................................................. 14

1.4

M u ..................................................................................................................... 14

1.5

dn in ring v dn in ng lng ....................................................... 14

2.2.1

dn in ring ................................................................................................. 14

2.2.2

dn in ng lng..................................................................................... 15

1.6

Quan h gia dn in ring v tc chuyn ng ca ion.............................. 16

1.7

Linh ion ............................................................................................................... 17

1.8

S ph thuc ca dn in vo nng dung dch cht in li .......................... 19

1.9

S vn ti.................................................................................................................. 22

1.10

Phng php o dn din v ng dng ............................................................... 25

2.7.1 Phng php o dn in................................................................................ 25

2.7.2

ng dng ca phng php o dn in ........................................................ 26

Chng 3 Th in cc v sc in ng ca pin in..................................................... 28

3.1

in cc v nguyn nhn sinh ra th in cc......................................................... 28

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

Phn loi in cc .................................................................................................... 32

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

in cc oxi ho kh (Redox) ............................................................................. 38

3.4.5

in cc oxit kim loi .......................................................................................... 38

3.5

S dng gi tr th in cc tiu chun xt chiu hng phn ng ......................... 40

3.6

Pin in (Pin Ganvani hoc mch in ha) ............................................................ 42

3.6.1

Pin in v cc phn ng xy ra trong pin ........................................................... 42

3.6.2

Sc in ng ca pin in .................................................................................. 43

3.6.3

Phn loi pin in................................................................................................. 44

3.7

Phng php o sc in ng v ng dng ........................................................... 46

Chng 4 Gin th in cc -pH ................................................................................... 50

4.1

M u ..................................................................................................................... 50

4.2

C s s liu xy dng gin E - pH................................................................ 50

1.10.1

H oxi ho kh thun tu ................................................................................. 50

1.10.2

H axit - baz thun tu ................................................................................... 51

1.10.3

H phn ng hn hp - C s trao i electron v c mt ion tham gia phn

ng.................................................................................................................... 52

4.3

Mt s gin E - pH (gin M. Pourbaix).......................................................... 53

4.3.1 Gin ca nc tinh khit 25oC ..................................................................... 53

4.3.2 Gin E - pH ca kim loi tip xc vi nc (Me - H2O) ................................ 55
Chng 5 n mn in ha hc.......................................................................................... 62

5.1

Nhng khi nim c bn .......................................................................................... 62

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

Hin tng n mn in ho v cc giai on ca qu trnh n mn in ho........ 63

5.3

Phng trnh ng hc in ho .............................................................................. 65

5.3.1 Phng trnh ng hc in ho xy ra trn in cc n................................... 65

5.3.2

S chuyn vt cht ............................................................................................... 72

5.3.3 Phng trnh ng hc ca qu trnh b khng ch hn hp ............................... 76

5.4

n mn in ho - h in cc phc tp xy ra nhiu phn ng ............................. 77

5.4.1

S n mn kim loi ng u trong mi trng axit ........................................... 77

5.4.2

Mt s yu nh hng n dng n mn im ........................................................ 82

5.5

Gin Evans xc nh tc n mn kim loi...................................................... 84

5.6

n mn in ho ca kim loi bi mi trng cht in li c mt oxi.................... 89

5.7

S th ng ho kim loi ......................................................................................... 92

5.7.1

Kim loi hot ng v kim loi th ng............................................................. 92

5.7.2

Cc phng php th ng ho kim loi.............................................................. 93

5.7.3

Hp kim v s th ng ho .............................................................................. 100

5.7.4 Thuyt th ng ho........................................................................................... 103

Chng 6 Cc dng n mn .............................................................................................. 104
1.11

n mn u ............................................................................................................ 104

1.12

n mn cc b ....................................................................................................... 104

1.12.1

n mn tip xc (cn gi l n mn Ganvanic) ............................................ 104

1.12.2

S n mn kim loi do s chnh lch kh ...................................................... 109

1.13

n mn l hay cn gi l n mn im (pitting corrosion) ................................... 113

1.14

Mt s dng n mn khc ...................................................................................... 115

6.5.1

n mn ranh gii ............................................................................................... 115

6.5.1

n mn nt do ng sut ..................................................................................... 116

6.5.1

n mn mi........................................................................................................ 117

6.5.1

n mn chn lc ................................................................................................ 117

6.5.1

n mn mi mn................................................................................................ 118

6.5.1

n mn do ma st............................................................................................... 118

1.15

nh hng ca mi trng n qu trnh n mn kim loi .................................. 118

6.5.1

n mn trong mi trng kh quyn.................................................................. 118

6.5.2

n mn kh quyn vng thnh ph v khu cng nghip.................................... 120

6.5.3

n mn trong kh quyn bin............................................................................. 120

6.5.4

n mn trong mi trng t............................................................................. 121

6.5.5

n mn trong btng ct thp............................................................................ 121

6.5.6

n mn vi sinh ................................................................................................... 123

Chng 7 S n mn vt liu kim loi v cc bin php bo v kim loi chng n mn

in ha ............................................................................................................. 125
7.1

La chn vt liu kim loi thch hp ..................................................................... 125

7.1.1

Kim loi en ....................................................................................................... 125

7.1.2

Gang ................................................................................................................... 127

7.1.3

Thp khng g..................................................................................................... 127

7.1.4

ng v hp kim ng....................................................................................... 129

7.1.5

Titan v hp kim titan ........................................................................................ 130

7.1.6

Niken v hp kim niken ..................................................................................... 131

7.1.7

Nhm v hp kim nhm..................................................................................... 131

7.2

X l mi trng bo v kim loi ...................................................................... 133

7.2.1 Loi tr cc cu t gy n mn .......................................................................... 133

7.2.2
7.3

S dng cht c ch bo v kim loi khi s n mn........................................ 134

Nng cao bn chng n mn kim loi bng cc lp sn ph ............................ 136

7.3.1 Ph kim loi ln b mt kim loi........................................................................ 136

7.3.2

Lp ph v c .................................................................................................... 139

7.3.3

Lp ph hu c .................................................................................................. 141

7.3.4

Lp ph cht do................................................................................................ 142

7.4

Bo v kim loi chng n mn kim loi bng phng php in ho ................... 142

7.4.1 Phng php bo v catot bng dng ngoi....................................................... 143

7.4.2

Bo v bng anot hy sinh ................................................................................... 144

7.4.3

Bo v anot......................................................................................................... 146

Chng 8 Cc phng php xc nh tc n mn kim loi...................................... 147

8.1

M u ................................................................................................................... 147

8.2

Cc phng php xc nh tc n mn kim loi ............................................... 148

8.2.1 Phng php trng lng................................................................................... 148

8.2.2 Phng php th tch.......................................................................................... 149
8.2.2

Cc phng php phn tch................................................................................ 149

8.2.3 Phng php in ho ........................................................................................ 149

Ti liu tham kho............................................................................................................ 183

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

kinh t ca mt quc gia, c bit i vi cc nc c nn cng nghip ang pht trin. Vy

vic nghin cu v n mn v bo v kim loi l mt vn rt c ngha v khoa hc v
thc tin.
V nh ngha n mn kim loi c th pht biu nhiu dng khc nhau. Xin n c mt
s cch pht biu sau y:
Trn quan im nhn nhn vn n mn kim loi l s ph hu kim loi v gy ra thit
hi th: s n mn kim loi l qu trnh lm gim cht lng v tnh cht ca kim loi do s
tng tc ca chng vi mi trng xm thc gy ra.
Song cng cn phi lu rng do mc ch hon thin sn phm th i khi hin tng n
mn li c tc dng tch cc. V d s oxi ho nhm to ra b mt nhm c lp oxit nhm
bn vng chng li s n mn tip theo ca nhm do mi trng gy ra, mt khc cn lm
tng v p, trang tr cho sn phm. Vic x l b mt kim loi bng phng php ho hc
hoc in ho lm tng bng ca sn phm, n gn lin vi s ho tan b mt kim loi
(nh bng cc sn phm thp khng g, nh bng cc vt m trc khi m in v.v...).
Trong iu kin th c th dng nh ngha sau y v s n mn kim loi:
n mn kim loi l mt phn ng khng thun nghch xy ra trn b mt gii hn gia
vt liu kim loi v mi trng xm thc c gn lin vi s mt mt hoc to ra trn b
mt kim loi mt thnh phn no do mi trng cung cp.
Nu xem hin tng n mn kim loi xy ra theo c ch in ho th s n mn kim loi
c th nh ngha nh sau:
n mn kim loi l mt qu trnh xy ra phn ng oxi ho kh trn mt gii hn tip xc
gia kim loi v mi trng cht in li, n gn lin vi s chuyn kim loi thnh ion kim
loi ng thi km theo s kh mt thnh phn ca mi trng v sinh ra mt dng in.

1.2 Tm quan trng v mt kinh t ca vn n mn kim loi

Vn n mn kim loi c lin quan n hu ht cc ngnh kinh t. Ngi ta tnh
c rng gi tin chi ph cho lnh vc n mn chim khong 4% tng thu nhp quc dn i
vi nhng nc c nn cng nghip pht trin.
Chi ph ny tnh cho cc khon sau:
Nhng mt mt trc tip: Tin chi ph cho vic thay th cc vt liu b n mn v
nhng thit b xung cp do n mn gy ra.
Nhng tn tht gin tip: Chi ph cho vic sa cha s lng sn phm gim cht lng
trong qu trnh sn xut hoc b mt mt do hin tng n mn kim loi gy ra.
Chi ph cho cc bin php phng nga, cc bin php bo v chng hin tng n
mn kim loi.
Thng thng, chi ph trc tip t hn rt nhiu so vi chi ph gin tip. V vy, vic
nghin cu bo dng v bo v chng n mn, ko di thi gian s dng cc thit b, my
mc, cc cu kin, cu cng, tu bin, cc cng trnh ven bin... thng xuyn l mt vn
rt c ngha v mt khoa hc k thut cng nh v mt kinh t.

1.3 Nhng khi nim c bn

1.3.1 Cc phn ng n mn kim loi
n mn kim loi l phn ng oxi ho kh bt thun nghch c xy ra gia kim loi v
mt cht oxi ho c trong mi trng xm thc. S oxi ho kim loi gn lin vi s kh cht
oxi ho. C th cng thc ho s n mn kim loi nh sau:
Kim loi + cht oxi ho kim loi b oxi ho + cht kh
V d:
Fe + 2HCl FeCl2 + H2

(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)

ng nhin trong mi trng axit nu nng oxi thp th s n mn kim loi ch yu

gn lin vi phn ng gii phng kh hiro.
Trong iu kin nhit thng v khng kh m xy ra s n mn kim loi v c gi
l n mn m. Cc cht oxi ho trong mi trng n mn l: nhng proton b xonvat ho hoc
l lng oxi b ho tan vo mi trng n mn. Ngoi ra cn c mt s cht oxi ho khc
cng gy ra s n mn kim loi, v d:
Cc cation kim loi: Cu2+, Fe3+, Sn4+;
Cc anion: NO2, NO3, CrO42, MnO4, OCl;
Cc cht kh ho tan vo mi trng n mn: O2, SO2, Cl2.
nhit cao, s n mn kim loi xy ra l do tc dng ho hc gia kim loi v cc
cht oxi ho dng kh v cn gi l s n mn kh. Cc cht kh c tc dng ph hu kim
loi nhit cao: kh O2, hi nc, kh CO2, kh SO2 v.v...
Trong qu trnh xy ra s n mn kim loi, phn ng oxi ho kh lun bao gm hai phn
ng ring bit gi l phn ng ring phn: phn ng oxi ho gi l phn ng ring phn anot
hay l phn ng anot v phn ng kh gi l phn ng catot. T phn ng (1.3) c th vit:
Fe Fe2+ + 2e

phn ng anot

2H+ + 2e H2

phn ng catot

Phn ng chung: Fe + 2H+ Fe2+ + H2

(1.5)

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.

1.3.2 nh lut Faraday

Theo nh lut Faraday, khi c ni mol ca mt cht i no trong bnh in phn c
to thnh hay l mt i th t l vi mt in lng Q i qua mt gii hn ca in cc v
dung dch cht in li.
Q = ZFni

(1.6)

trong : F = 96493 C/mol; Z: s electron trao i.

V d: Theo phn ng (1.3), s ho tan anot ca st vi Z = 2.
Nu thc hin php vi phn phng trnh (1.6) theo thi gian, ta nhn c biu thc sau
y (dng khc ca nh lut Faraday) c dng rt ph bin:
dQ
dt

= ZF

dn i
dt

=I

(1.7)

I: cng dng in (ampe - A)

dn i

hoc
dn i
dt

dt

(1.8)

ZF

: tc phn ng (mol/s)

Vy theo nh lut Faraday th tc phn ng t l vi cng dng in i qua mt

gii hn pha gia in cc v cht in li.

1.3.3 Pin in ha v bnh in phn

Pin in ho: Pin in ho l mt h gm hai in cc c s tip xc gia cc dung
dch cht in li v gia chng c ni vi nhau bng dy dn electron. V d pin Daniel Jacobi:
() Cu Zn ZnSO4 CuSO4 Cu (+)

(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)

Phn ng chung: Zn + Cu2+ Zn2+ + Cu

(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)

in cc Pt l vt liu tr ho hc, khng tham gia phn ng.

Pin (1.13) c m t trn hnh 1.1:
A
O2
H2

2
1

Hnh 1.1
Pin hiro oxi
1. Dung dch axit H3PO4 hoc H2SO4;

2. Cc tm Pt lm in cc (tm Pt c din tch ln hp ph cc kh H2

v O2)
Khi khp kn mch pin hiro v oxi xy ra cc phn ng:
() anot:

2H2 4e 4H+

(1.14)

(+) catot:

O2 + 4H+ + 4e 2H2O

(1.15)

Phn ng chung: O2 + 2H2 2H2O

Vy khi pin lm vic phn ng hnh thnh nc t kh hiro v oxi din ra mt cch t
din bin ng thi sinh ra dng in.
Cng dng in i qua pin t l trc tip vi s mol kh H2 v kh O2, phn ng trn
cc in cc vi Z = 4 v Z = 2 ng vi oxi v hiro.
Vy:

I = 4F

dnO2
dt

= 2F

dn H2
dt

(1.16)

10

T pin in (1.13) phn t nc c to thnh do s kt hp ca cc phn t H2 v O2.

Song ngc li, t phn t nc bng con ng in phn dung dch axit H3PO4 hoc H2SO4
vi cc in cc tr ta li thu c cc kh H2 v O2 (xem hnh 1.2), ng vi cc phn ng in
cc.
(+) anot:

2H2O O2 + 4H+ + 4e

() catot:

4H+ + 4e 2H2

Phn ng chung: 2H2O O2 + 2H2

S mol kh O2 v H2 c to ra t l vi lng in t bn ngoi i qua bnh in phn.
Quan h gia chng tun theo nh lut Faraday.
Cn phi lu rng: trong bnh in phn anot ng vi cc dng (+) cn trong pin in
th anot ng vi cc m (). Trong hai trng hp c s ngc nhau, song cn phi nh rng
anot l ni xy ra ca phn ng oxi ho, cn trn catot lun lun xy ra phn ng ca s kh.

O2

H2

Hnh 1.2
Bnh in phun nc iu ch H2 v O2

1. Dung dch axit H3PO4 hoc H2SO4;

2. Cc in cc Pt; A. ng h ampe

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

n mn nh x (local corrosion): n mn nh x l s ph hu kim loi ti mt ch

(hoc l mt vng) no trn b mt kim loi, ti l vng anot (xem hnh 1.3b).
Trong thc t cng nghip, n mn nh x xy ra ph bin hn nhiu so vi n mn
ng u.
n mn nh x hot ng nh l mt pin in, ta c th m phng hin tng n mn
nh x i vi kim loi st trong mi trng axit bng cch to ra pin n mn sau y (xem
hnh 1.4):
e
A

H2

Fe

Pt
1

Hnh 1.4
Pin n mn Fe - Pt

trong dung dch axit

1. Dung dch axit

S n mn nh x (xem h.1.3b) c th c m phng nh l mt pin n mn (xem

h.1.4), trong vng catot v anot c tch ra. Phn ng catot trn hnh 1.4 l s gii phng
hiro trn in cc platin:
2H+ + 2e H2
Ti anot st b n mn v ho tan thnh ion chuyn vo dung dch:
Fe 2e Fe2+ km theo s gii phng kh H2 trn catot.
v phn ng tng cng l:
Fe + 2H+ Fe2+ + H2
C th ni rng hot ng n mn ph hu kim loi do mi trng gy ra ph thuc vo
rt nhiu yu t:

12

Thnh phn ha hc, vi cu trc ca kim loi;

Thnh phn ha hc ca mi trng;
Cc thng s vt l - nhit ; s i lu; s pht x v.v...
Nhng tc ng c hc - s va p; ma st; ng lc v.v...
Vy bn chng n mn ca kim loi khng hon ton ph thuc vo tnh cht vn c
ca kim loi m ch yu ph thuc vo tnh cht ca mt gii hn kim loi - mi trng v tt
nhin l ph thuc vo thnh phn ho hc, trng thi cu trc cng nh tnh cht in ho
ca mt gii hn pha. Vy s n mn kim loi din ra rt phc tp v a dng. Sau y l mt
s dng n mn in hnh thng gp c phn loi da vo trng thi b mt kim loi b
ph hu (xem hnh 1.5).
a) n mn ng u (uniform corrosion): l s mt i mt lng t hoc nhiu vt liu
kim loi c phn b mt cch ng u trn mi phn ca b mt kim loi tip xc vi mi
trng n mn (n mn kim loi do mi trng axit) (xem hnh 1.5a)
b) n mn Ganvani (galvanic corrosion): (pin n mn) cn c gi l n mn lng kim
loi, n xy ra l do s hnh thnh pin in t hai kim loi v khng ngng lm gim bn
kim loi (xem hnh 1.5b).
c) n mn hang hc (crevice corrosion): l do s hot ng ca pin in gm hai in
cc c to ra ti hai v tr trn kim loi tip nhn oxi vi mc khc nhau. Ti cc khe
kim loi hoc cc ch kim loi b che khut do gp khc, tip nhn oxi trong kh quyn vi
lng thp hn th n ng vai tr l anot, ti kim loi b ho tan (xem hnh 1.5c).
d) n mn im (pitting corrosion): Dng n mn ny thng xy ra trn b mt kim loi
c bo v bng mt lp mng mng (Al2O3/Al) tip xc vi dung dch cht in li c mt
mt s anion v ch yu l anion clo. Anion tc dng ln mng mng to ra cc l nh c
kch thc c vi chc micr mt v lm mt tnh bo v ca mng dn n s ph hu kim
loi (xem hnh 1.5d).
e) n mn ven tinh th (intergranular corrosion): l s ph hu kim loi c tnh chn lc
ti ch ni cc ht tinh th, v l mt pha c kt tinh li do x l nhit to ra (xem hnh
1.5e).
f) n mn chn lc (selective corrosion): l s oxi ho mt thnh phn ca hp kim v
thng to ra mt cu trc kim loi xp (xem hnh 1.5f).
g) n mn mi mn (erosion corrosion): l s n mn kim loi gy ra do tc ng c hc
vo b mt kim loi. V d s n mn xy ra ti ch kim loi c dng cht lng chy qua rt
nhanh (xem hnh 1.5g).
h) n mn ng lc (stress corrosion cracking): s rn nt kim loi do tc ng ng thi
ca s cng bc c hc v xy ra phn ng in ho khi kim loi tip xc vi mi trng n
mn. V d s rn nt ca my bay, s rn nt ca cc ni phn ng ho hc lm vic p
sut cao v.v...

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.

1.5 dn in ring v dn in ng lng

2.2.1 dn in ring
dn in ring ca dung dch cht in li cho l dn in ca n c t gia
hai in cc song song c din tch 1 cm2 v cch nhau 1 cm.
dn in ring l i lng nghch o ca in tr sut.
=

(2.1)

tm n v o ta xt in tr ca mt ng dung dch cht in li tng t mt dy

dn kim loi c chiu di l (cm) v tit din
S (cm2), in tr sut ca dy kim loi l .
Vy in tr R ca dy dn c tnh:
R = .
Suy ra:

(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

Gi tr h s k thay i tu thuc vo bn cht dung dch, i vi dung dch axit mnh k

= 0,0164, i vi dung dch baz mnh k = 0,0190, i vi dung dch mui k = 0,022.

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)

trong C l nng ng lng gam/lit.

T suy ra n v o ca bng 1.cm2.lg1.
Nu t V =

1
C

gi l pha long th cng thc (2.5) c dng:

= 1000.V.

(2.6)

T phng trnh (2.5) cho thy khi dung dch rt long (C 0) th gi tr t n gi

tr ti hn .
i vi dung dch cht in li yu, s ph thuc ca dn in ng lng vo
nng cht in li thc cht l ph thuc vo s bin i in li (hnh 2.1).
C = .

Vy:
Suy ra:

(2.7)

(2.8)

trong : C dn in ng lng ca dung dch c nng C.

Hnh 2.1
S ph thuc ca dn in ng lng vo pha long V

16

1.6 Quan h gia dn in ring v tc chuyn ng ca ion

Trong trng hp n gin ta hy xt mt ng dung dch cht in li 1-1 (v d KCl,
KNO3...). MA phn li thnh cc ion M+ v A.
Gi Uo - tc chuyn ng tuyt i ca cation M+
v Vo - tc chuyn ng tuyt i ca anion A.
Nu t ng dung dch vo in trng E (V/cm) th:
Tc chuyn ng ca cation:
U = Uo.E (cm/giy)

(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)

Di tc dng ca in trng, trong mt n v thi gian 1 giy s cation + v anion

i qua tit din S = 1 cm2 bng:

trong : C/ =

+ = C/ + NA.Uo.E

(2.11)

= C/ NA.Vo.E

(2.12)

C
1000

gi l nng ion trong mt n v th tch 1 cm3.

Uo v Vo l tc tuyt i ca cation v anion v chnh l di do cation di chuyn

trong 1 n v thi gian 1 giy vi E = 1 (V/cm).

Hnh 2.2
S di chuyn ca cc ion di tc dng ca in trng

Phng trnh (2.11) v (2.12) c th vit:

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.

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.
Cd lg/ l

= F (Uo + Vo)

(2.20)

Cc phng trnh (2.19) v (2.20) th hin mi quan h gia dn in ring v dn

in ng lng vi tc chuyn ng tuyt i ca cation v anion.

1.7 Linh ion

Tch s ca hng s Faraday v tc tuyt i ca cation Uo c gi l linh cation:
U = F . Uo
v linh anion:

(2.21)
V = F . Vo

(2.22)

Kt hp (2.22) v (2.20) ta c:
= (U + V)

(2.23)

i vi dung dch long C 0, 1 khi dn in ng lng c gi l

dn in ng lng nng v cng long v phng trnh (2.23) c dng:
= U + V

(2.23a)

trong U v V l linh cation v anion nng v cng long (cn gi l linh

ti hn) hoc:
= + +

(2.24)

18

+ v l dn in ng lng ca cation v anion nng v cng long (C

0).
Da vo cng thc (2.24) khi bit dn in ng lng ca ion ti nng v cng
long tnh c dn in ng lng phn t nng v cng long.
V d: Tnh ca axit axetic cho bit:
Cht in li

( .cm2.lg1)
1

HCl

CH3COONa

NaCl

426,00

91,00

126,50

Theo cng thc (2.24) ta c th vit:

(CH3COOH) = (H+) + (CH3COO)
= (HCl) + (CH3COONa) (NaCl)
= 426,00 + 91,00 126,50 = 390,6
Gi tr linh ti hn ca ion H3+ O v OH rt ln so vi cc cation v anion khc. Trong
mi trng nc cc ion ny chuyn ng theo c ch c bit - c ch truyn cho proton
gia chng v phn t HOH bn cnh.

H
O

H
O

H
+
O + H

H
O

Bng 2.1 Gi tr linh ti hn ca mt s cation v anion

Cation
Gi tr linh
V (25oC)
Anion
Gi tr linh
V (25oC)

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

Mt khc trong cng mt iu kin gi tr linh ti hn ca ion ph thuc vo nng ,

nhit v dung mi (xem bng 2.2).

19

Bng 2.2 Gi tr linh ti hn ca ion ph thuc vo mt s iu kin

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

1.8 S ph thuc ca dn in vo nng dung dch cht in li

dn in ca dung dch cht in li ph thuc vo ton b ion c mt trong dung dch,
ngha l ph thuc vo nng dung dch v in li .
i vi cht in li yu 1-1 vi nng C v in li :
AB U A + B+
Vy tng s ion trong mt n v th tch 1 cm3 bng:
+ + =

2..C.N A
1000

= const .C

(2.25)

Tng s ion trong mt n v th tch t l vi tch s .C.

i vi dung dch cht in li yu, trong dung dch m c in li rt nh. V vy,
nng ion t l vi tch s ca .C v trong dung dch khng c khi nim kh quyn ion. Khi
dung dch rt long, khong cch gia cc ion rt ln cho nn cc ion chuyn ng mt cch
c lp, dn in ng lng ca cc ion t gi tr ti hn + v .
dn in ring v dn in ng lng ca dung dch cht in li yu c tnh
theo cc phng trnh sau:
=
v

.C
1000

( + + )

= ( + + )

(2.26)
(2.27)

Kt hp vi (2.24) ta c:
=

(2.28)

Vy dn in ring ca cht in li yu ph thuc vo nng (xem hnh 2.3) song

s bin i ca n rt nh khi tng nng cht in li.

20

Hnh 2.3
S ph thuc ca dn in ring vo nng C

i vi cht in li mnh c lin kt ion, v d hp cht mui, mng tinh th ca n cu

to t cc ion v khi ho tan trong nc hoc trong cc dung mi c hng s in mi ln th
xung quanh ion lun hnh thnh cc lp v hirat (hoc xonvat) ngn cn s ti kt hp to
thnh cc phn t. Trong nhng mi trng cht in li b phn li hon ton hoc gn hon
ton ngay c khi nng cao v nng ion bng nng dung dch. Vy dn in ng
lng ca hp cht bng tng s dn in ng lng ca cc ion:
= + +

(2.29)

Vy dn in ng lng ca cc cht in li mnh trong dung dch nc ph thuc

vo nng c xc nh ch yu bng cc lc tng tc gia cc ion, ngha l vo khong
cch gia cc ion v bn cht ca mi trng.
S c mt ca nhng tng tc ny gy ra s km hm nht nh i vi s chuyn ng
ca cation v anion, ngha l lm gim linh ca chng khi tng nng .
Gi l dn in ng lng ti hn ca dung dch cht in li mnh trong dung
dch rt long khng tnh n tng tc gia cc phn t trong dung dch. Ti nng xc
nh, dn in ng lng (2.29) lun lun nh hn v bng:
= I II

(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

H s a ph thuc vo bn cht dung mi, ngha l vo hng s in mi cng nh

nht ca n, vo nhit . C th xc nh n bng thc nghim hoc tnh trn c s l thuyt
dung dch.
Cng cn phi nhn mnh rng, i vi dung dch cht in li mnh rt long C 0 th
v trong dung dch khng cn tn ti kh quyn ion v c th vit:
= + +

(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)

+ +

H s dn ph thuc vo ho tr ca cc ion (xem bng 2.3).

Bng 2.3 Gi tr h s dn f ph thuc vo ho tr ion
Loi dung dch cht in li vi nng 0,1N

1-1

1-2

1-3

Gi tr f

0,8

0,75

0,4

Khi dung dch rt long, lc tng tc tnh in rt nh, tc dng km hm rt nh v c

th b qua s khc bit ca f ph thuc vo ho tr ion.
dn in ring ca cht in li mnh ph thuc vo s ion trong 1 cm3 dung dch v
tc tuyt i ca chng. Khi tng nng th s ion trong 1 cm3 dung dch tng ln song
tc tuyt i gim. S tng quan gia cc yu t dn n s xut hin dn in
ring cc i (xem hnh 2.3).
Vic so snh nh hng ca nng n dn in ng lng ca cc cht in li
mnh v yu c th hin trn cc ng cong biu din s ph thuc ca vo nng C
(hnh 2.4) v vo C (hnh 2.5).

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

Cht in li mnh c dn in ng lng rt ln ngay c i vi dung dch m dc.

Khi tng pha long dn in ng lng tng.
Trong min dung dch long s ph thuc ca vo C i vi cht in li mnh c
quan h tuyn tnh v tun theo phng trnh (2.31) (xem hnh 2.5).
i vi dung dch cht in li yu, ngay c khi nng rt long gi tr dn in
ng lng cng rt nh v ch khi nng rt nh C 0 th n tng t ngt t n gi
tr ti hn . Trn hnh 2.5 cng cho thy s ph thuc v C i vi cht in li yu l
tuyn tnh ti vng nng rt nh.
Da vo ng cong trn hnh (2.5) cho php ngoi suy v tnh c i vi cht in
li mnh (i vi dung dch KCl, LiCl).

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

- S ng lng cht bin i trn in cc,

g - Lng cht thot ra hoc mt i trn in cc (gam),
a - ng lng cht tnh theo gam v a = A/Z, trong A l khi lng phn
t (hoc nguyn t tnh theo gam), Z l s electron tham gia phn ng (hoc s oxi
ho - ho tr ca ion);
I - Cng dng in (Ampe) i qua bnh in phn;
t - Thi gian (giy) in phn.
Vy t (2.34) ta c:
g=

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)

t+ l s vn ti cation bng t s tc tuyt i ca cation so vi tng tc tuyt i

ca hai loi ion (hoc biu din qua linh ion).
Tng t t l s ti anion chnh bng t s tc tuyt i ca anion so vi tng tc
tuyt i ca c hai loi ion (hoc biu din qua linh ion).
t =

Uo

U
=
=
U o + Vo
U+V
+ +

t+ + t = 1

Vy

(2.37)

(2.38)

Da vo s bin i nng ti cc khu vc catot v anot c th xc nh c s ti.

Xt qu trnh in phn vi cc in cc tr (platin). Gi thit chia bnh in phn thnh
ba khu vc - khu catot, khu gia v khu anot (xem hnh 2.6).

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

, ngha l khi xy ra in phn

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
n c

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)

- dn in ng lng ca phn t nng v cng long.

25

1.10 Phng php o dn din v ng dng

2.7.1 Phng php o dn in
S dng cu o bng dng xoay chiu xc nh dn in ca dung dch cht in li
(xem hnh 2.7).

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

= 1. iu chnh RM sao cho khng c

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

Vy

Rx

R1
R2

= 1 RM = Rx

Rx - l in tr ca bnh o in ho gm hai in cc platin ph kim loi platin c din

tch hnh hc 1cm2 v cch nhau 1 cm, trong cha dung dch cht in li cn xc nh in
tr.
Cc in tr R1 v R2 c chn trc.
in tr mu RM (bin i).
Rx - in tr bnh o dn.
Theo cng thc (2.3) dn in ring ca dung dch in li c tnh:
=
K=

A
S

1
Rx

A
S

K
Rx

[cm1] gi l hng s bnh.

Rx c xc nh bng thc nghim, bit hng s K l tnh c .

(2.43)

26

xc nh hng s K phi s dng dung dch chun KCl 0,02N c gi tr bit, =

0,002765 1.cm1 25oC. Bng thc nghim o in tr RKCl ca dung dch 0,02N KCl v
suy ra hng s K:
K = 0,002765.RKCl
Theo phng trnh (2.43), bit hng s K c th o c in tr Rx ca dung dch cht
in li bt k v suy ra dn in ring .

2.7.2 ng dng ca phng php o dn in

Phng php o dn in c rt nhiu ng dng trong nghin cu v thc t, di y
xin nu hai trng hp.
a) Xc nh tan mui t tan
i vi dung dch mui t tan, tan S (tnh theo s ng lng gam c trong mt lt
dung dch) chnh bng nng C (lg/A hoc mol/l) ca mui t tan trong dung dch. tan
rt nh v xem dung dch l v cng long khi dn in ng lng ca dung dch
c tnh bng:
=

1000.
S

S=

1000.

(2.44)

o gi tr , - dn in ng lng nng v cng long cho trc ( = U +

V), t suy ra S.
b) Chun bng phng php o dn in (chun dn in k)
Nguyn tc ca vic chun dn in l l o dn in ring theo di s thay th ion
c linh ion ln (H+) bng ion c linh b hn (OH) hoc ngc li. T xc nh im
tng ng cho qu trnh chun .
V d: Chun dung dch axit mnh HCl bng baz mnh NaOH (xem hnh 2.8).
Phn ng xy ra trong qu trnh chun :
HCl + NaOH = H2O + NaCl
+

H + OH = HOH

(2.45)
(2.46)

Ti im A - ng vi nng ban u ca ion H+ c gi tr ln nht. Theo s tng dn

s ml dung dch NaOH cho vo dung dch axit ban u xy ra phn ng (2.45), (2.46), nng
ion H+ gim do dn in gim, c gi tr cc tiu khi [H+] = [OH].

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

Cho d [OH ] th dn in tng theo ng OB. im O c xc nh bng cch

ngoi suy 2 on thng AO v BO, v gi l im tng ng ca php chun . ng
thng OB lun lun c dc nh hn OA l v linh ion H+ ln hn linh OH.
ng AOB biu din s bin i ca dn in ring ph thuc vo s ml dung
dch NaOH trong qu trnh chun axit yu bng baz mnh.
Axit yu phn li thnh H+ vi rt nh, vy nng H+ rt nh v dn in rt
nh (im A). Khi thm dung dch NaOH vo dung dch axit yu, dung dch axit yu b
long ra v th nng [H+] v nng [Na+] tng ln v dn n s tng dn gi tr dn
in theo on thng AO.
Tng dn nng OH , khi OH d v dn in ca dung dch tng theo OB.
dc on thng OB ln hn OA v linh OH ln. im ngoi suy O ct nhau ca 2
on thng AO v OB chnh l im tng ng ca qu trnh chun .

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

a) S di chuyn ca ion Ag+ (t kim loi) vo trong dung dch;

b) Lp in kp trn b mt gii hn pha; c)S phn b th theo chiu dy lp in kp
+
Trn hnh 3.1a m t s dch chuyn ion Ag+ trn b mt kim loi ( Ag KL
) i vo dung
+
dch AgNO3, thot u ion Ag KL i vo dung dch vi tc ln v li electron trong kim
+
loi. V b mt kim loi Ag d in tch m nn ion Ag KL
th 2 i vo dung dch kh khn
hn, tip theo sau cc ion th 3, th 4 i vo trong dung dch cng kh khn hn na.
Ngc li, theo thi gian nng ion Ag+ gn st b mt kim loi tng dn ln v lm d
dng cho cho s dch chuyn ion Ag+ t dung dch i vo b mt kim loi. Sau mt thi gian
+
nht nh trn b mt gii hn pha t trng thi cn bng ca hai qu trnh ion Ag KL
i vo
+
dung dch v ion Ag t dung dch i vo trong kim loi. Khi h t trng thi cn bng, trn
b mt gii hn hnh thnh lp in kp, vi hai bn tch in ngc du v chiu dy lp kp
c bn knh nguyn t () (xem hnh 3.1c). Do c lp in kp sinh ra th in cc E, s
phn b th in cc ca lp in kp trn mt gii hn pha theo chiu dy ca lp d l tuyn
tnh (hnh 3.1c).

Lp in kp gi tt l lp kp trn hnh 3.1b cn gi l lp kp c - lp kp Helmholtz

- lp kp ny ch yu l do lc tng tc tnh in v c p dng cho cc dung dch tng
i m c
Khi dung dch tng i long v tnh n s chuyn ng nhit cc ion gn b mt in
cc, th s phn b th ca lp kp theo chiu dy lp kp gm 2 phn: phn tuyn tnh v
phn khng tuyn tnh.

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

Trong trng hp ny Stern chia lp kp thnh 2 phn:

+ Phn Helmholtz - Cn gi l lp kp c (c k hiu l (*) trn hnh 3.2b).
+ Phn khuch tn - Phn Goui- Chapman (c k hiu (**) trn hnh 3.2b).
Nghin cu v cu trc lp kp l mt vn rt hp dn cc nh in ha, v n c
ngha khoa hc rt ln, song c nhng hn ch nht nh v lp kp rt phc tp. Vn ny
c trnh by y hn trong cc gio trnh chuyn .

3.3 S ph thuc ca gi tr th in cc vo nng cht phn ng,

phng trnh Nernst
Trn b mt gii hn pha cht dn in loi 1 v loi 2 ca in cc xy ra phn ng oxi
ha kh dng:
i Oxi + Ze U i Redi

(3.1)

Khi i = 1 ta c:
Oxi + Ze U Redi

(3.2)

V d trn in cc Cu2+/Cu xy ra phn ng :

Cu2+ + 2e U Cu

(3.3)

Gia bin thin ha th U ca phn ng (3.3) v th in cc E quan h vi nhau theo

phng trnh:
U = AMax = Z.F.E
trong : Z l s electron trao i;
F l hng s Faraday (96493 C);
AMax l cng cc i hu ch.
p dng phng trnh (3.4) cho phn ng (3.3) ta c:

(3.4)

31

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.
U = Cu2 + + 2e Cu

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

gi l th in cc tiu chun ( 25oC).

ZF

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:
E=E +

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

trong k hiu l tch s cc hot .

V d vit phng trnh Nernst cho cc in cc sau:
Zn2+/Zn vi phn ng in cc Zn2+ + 2e U Zn 25oC:
EZn2 +

Zn

= EoZn2 +

0,059
2

Zn

lg

a Zn2 +
a Zn

Fe3+, Fe2+/Pt vi phn ng in cc Fe 3+ + 1e U Fe2+ 25oC:

EFe3 +

Fe2 +

o
= EFe
3+

+
Fe2 +

0,059
1

lg

aFe3 +
aFe2 +

O2(Pt)/H2O vi phn ng in cc O2 + 4e + 4H+ U 2H2O

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

Trong in ha c nhiu cch phn loi in cc v c th chia thnh mt s loi chnh

nh sau:

3.4.1 in cc loi 1

33

in cc loi 1 l in cc lm vic thun nghch vi cation. a s cc in cc gm kim

loi nhng vo dung dch mui ca n u thuc in cc loi 1 v c th vit dng tng
qut sau:
Men+/Me vi phn ng in cc:
Men+ + ne U Me

(3.9)

Phng trnh Nernst c dng:

EMen +

Me

= EoMen +

0,059

Me

lg

a Men +

25oC

a Me

(3.10)

V d 1: Zn2+/Zn hoc (ZnSO4/Zn) vi phn ng in cc:

Zn2+ + 2e U Zn
25oC ta c:

EZn2 +
EZn2 +

Zn

= EoZn2 +

0,059

Zn

0,059

= 0,76 +

Zn

a Zn2 +

lg

a Zn

lg a Zn2 +

V d 2: Cu2+/Cu hoc (CuSO4/Cu) vi phn ng in cc:

Cu2+ + 2e U Cu
25oC ta c:

ECu2 +
ECu2 +

Cu

o
= ECu
2+

0,059

Cu

= 0,34 +

0,059
2

Cu

lg

aCu2 +
aCu

lg aCu2 +

V d 3: Fe2+/Fe hoc (FeSO4/Fe) vi phn ng in cc:

Fe2+ + 2e U Fe
25oC ta c:

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

trong TAg l tch s tan ca mui AgCl, phng trnh Nernst i vi in cc bc

25oC l:
= EoAgCl

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

= 0,2224 V NHE khi CCl = 1M

= 0,2224 0,059 lg CCl

Gi tr th in cc bc ph thuc vo nng ion Cl (bng 3.1).

Bng 3.1 Gi tr th in cc bc ph thuc vo nng ion Cl 25oC
in cc

Gi tr th (V) v NHE

1,00N KCl, AgCl/Ag

0,2384

0,10N KCl, AgCl/Ag

0,2900

0,10N HCl, AgCl/Ag

0,2890

Trng hp tng qut i vi in cc loi 2 l: X, MexXy/Me, trong X l halogen,

phng trnh Nernst 25o C l:
= EoMex X y

EMex X y

Me

Me

0,059
y

(3.12)

lg a y
X

V d 2: in cc calomen, in cc ny c s Cl, Hg2Cl2/Hg.

Phn ng in cc: Hg2Cl2 + 2e U 2Hg + 2Cl
p dng cng thc 3.12, gi tr th in cc calomen c xc nh theo phng trnh:
EHg 2Cl2

hoc

EHg 2Cl2

Hg

Hg

o
= EHg
2Cl 2

Hg

0,059 lg CCl

(3.13)

= 0,2768 0,059 lg CCl

Gi tr th in cc calomen thay i theo hot ion Cl v ph thuc nhit .

Bng 3.2. S ph
vo nng ion Cl v nhit

thuc

ca

gi

tr

th

in

cc

calomen

35

Nng dung dch KCl

Gi tr th in cc trong khong 0o 100oC

0,1N

EHg 2Cl2

1,0N

EHg 2Cl2

Bo ha

EHg 2Cl2

= 0,336 7.105(t 25oC)

Hg

= 0,2801 2.104(t 25oC)

Hg

= 0,2412 7.105(t 25oC)

Hg

in cc calomen (xem hnh 3.4) cho gi tr th rt n nh, do c dng ph bin,

song v s dng thy ngn nn ngy nay c xu hng thay th in cc calomen bng in
cc bc.

8
6

4
3
2

2
1

Hnh 3.3

Hnh 3.4

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. Dy bc kim loi; 4. Dy dn in;

4. Thy ngn; 5. Dy platin;

5. L b sung dung dch; 6. L xp

6. Dy dn in; 7. Dung dch KCl;

8. L np dung dch KCl

V d 3: in cc thy ngn sunfat, Hg2SO4/Hg.

Phn ng in cc l: Hg2SO4 + 2e U 2Hg + SO42
Phng trnh Nernst tnh gi tr th in cc:
EHg 2SO4

= 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

V d 1: in cc hiro (xem hnh 3.5).

S in cc hiro: Hx+/H2(Pt)
Phn ng xy ra trn in cc:
2H+ + 2e U H2
C th xem in cc hiro l in cc lm vic thun nghch vi cation.
Phng trnh Nernst tnh gi tr th in cc 25oC:

E2H+

=
H2

o
E2H
+

+
H2

0,059
2

lg

a2H+
PH2

(3.15)

Nu p sut ca kh hiro bng n v PH2 = 1 atm v aH+ = 1 th ta c:

37

E2H+

H2

o
= E2H
+

= 0,0000 V
H2

v gi l th in cc tiu chun ca hiro.

Ngi ta dng in cc tiu chun hiro xc nh th in cc tiu chun ca cc in
cc khc. V vy ta c bng gi tr th in cc tiu chun ca cc in cc theo thang hiro
(k hiu l NHE hoc SHE), khi PH2 = 1 atm phng trnh 3.15 c dng:
E2H+

= 0,059pH

(3.16)

H2

hoc t rH = lg PH2 ta c:
E2H+

= 0,059 + 0,0295rH

(3.17)

H2

in cc ny cng knh, d b ng c lm sai lch gi tr th in cc. Ngy nay ngi

ta c th thay n bng in cc calomen, do c thang th calomen (SCE) hoc thay bng
in cc bc v ta cng c thang chun theo in cc bc.
V d 2: in cc kh oxi
Cu to in cc oxi: OH / O2(Pt)
Khc vi in cc hiro, in cc oxi l in cc khng thun nghch v oxi c th phn
ng vi kim loi b hp ph.
Phn ng in cc trong mi trng kim:
O2 + 4e + 2H2O U 4OH

(3.18)

= 0,401 V (NHE)

o
EO
2
OH

Trong mi trng axit:

O2 + 4e + 4H+ U 2H2O
o
EO
2

(3.19)

= 1,229 V (NHE)
H2O

V mt ng hc cc phn ng trn u c xem l thun nghch, do th cn bng

ca chng ng vi cc gi tr sau:
i vi phn ng (3.18):
o
EO
2

= 0,401 + 0,059 lg
OH

PO1 2/ 4

(3.20)

aOH

i vi phn ng (3.19):
o
EO
2

H2O

1/4

= 1,229 + 0,059 lg aH+ .PO2

(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+

; nu t lg PO2 = rO th cc phng trnh (3.20) v (3.21) c dng:

EO2

= 1,229 0,059pH 0,0148rO

(3.22)

H2O

3.4.4 in cc oxi ho kh (Redox)

in cc oxi ho kh l mt h in ho gm mt dy dn kim loi tr (v d Pt) tip xc
vi dung dch cha cht oxi ho kh.
V d 1: in cc oxi ho kh thun tu, trong dung dch ch c mt h oxi ho kh Fe3+,
Fe /Pt vi phn ng in cc:
2+

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 +

Trong trng hp tng qut:

Ox + Ze U Red
v

EOx

Re d

o
= EOx

0,059
Z

Re d

lg

aOx

(3.24)

a Re d

V d 2: in cc oxi ho kh hn hp. i vi trng hp ny, trong dung dch ngoi

cc cht oxi ha v kh cn c cc cht ng vai tr l mi trng phn ng, v d H+ hoc
OH.
V d: in cc MnO4, Mn2+, H+/Pt
Phn ng in cc:
MnO4 + 5e + 8H+ U Mn2+ + 4H2O

(3.25)

Phng trnh Nernst tnh th in cc 25oC :

EMnO ,H+
4

hoc

Mn2 +

EMnO ,H+
4

3.4.5

EoMnO ,H+
4

+
Mn2 +

0,059
5

lg

a MnO .a8H+
4

a Mn2 + .a4H2O

= 1,507 0,0945pH + 0,0118 lg

Mn2 +

in cc oxit kim loi

in cc oxit kim loi c cng thc MexOy/Me, OH.

a MnO

a Mn2 + .a4H2O

39

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
Sb,OH

o
= ESb
2O3

0,059 lg aOH

Sb,OH

(3.27)

i vi mi trng axit in cc ny c cu to: Sb2O3, H+/Sb hoc Sb(OH)3, H+/Sb vi

phn ng in cc:
Sb2O3 + 6e + 6H+ U 2Sb + 3H2O
Phng trnh Nernst tnh th in cc ca in cc ny 25oC:
ESb O
2

3 .H

Sb

o
ESb
+
2O3 .H

0,059

Sb

lg

aSb2O3 .a6H+
2
aSb
.a3H2O

Nu chp nhn aSb2O3 = 1, aSb = 1 v aH2O = 1 th ta c:

ESb O
2

3 .H

o
= ESb
O .H+

Sb

0,059pH

(3.28)

Sb

V d 2: in cc oxit thu ngn, cu to ca in cc: HgO/Hg, OH.

Phn ng in cc:
HgO + 2e + H2O U Hg + 2OH
hoc

HgO + 2e + 2H+ U Hg + H2O

Phng trnh gi tr th in cc 25oC:

EHgO

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)

C th dng in cc ny lm in cc so snh nu mi trng c pH > 7, cn trong mi

trng axit th oxit thu ngn b ho tan.

40

3.5 S dng gi tr th in cc tiu chun xt chiu hng phn ng

Bng gi tr th in cc tiu chun c gii thiu trong phn ph lc bao gm cc gi
tr th in cc tiu chun khc nhau v chng c xp theo chiu tng gi tr th in cc,
s dch chuyn t gi tr m nht n gi tr dng nht (t 3,02 V 3,06 V).
Cp oxi ho kh c th tiu chun cng m th cht kh ca cp cng d dng nhng
in t v kh nng nhn in t ca cht oxi ho cng km.
Hy xt chiu hng ca phn ng oxi ho kh xy ra khi trn 2 cp oxi ho kh vo
nhau. V d xt hai cp oxi ho kh Ce4+/Ce3+ v Fe3+/Fe2+ ng vi cc gi tr th tiu
chun 1,61 V v 0,77 V. Phn ng ring ca cc cp l:
Ce4+ + e U Ce3+
T th cn bng ca n 25oC bng:
ECe4 +

= 1,61 + 0,059 lg
Ce3 +

aCe4 +

(3.30)

aCe3 +

Fe3+ + e U Fe2+

Vi th cn bng 25oC bng:

EFe3 +

= 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 +

Ce4+ + Fe2+ U Ce3+ + Fe3+

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

Ti trng thi cn bng:

Fe + Cu2+ U Fe2+ + Cu
v cc phng trnh (3.32) v (3.33) bng nhau ta c:
0,4402 +
vi

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+

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:

Na + HOH = Na+ + OH +

1
2

H2

V d 2: Cho Ti2+ trong cp oxi ha kh Ti3+/Ti2+ vi

= 0,37 V, khi

EoTi3 +
Ti

2+

cho vo nc s phn hy nc gii phng hiro:

Ti2+ + HOH = Ti3+ +OH +

1
2

H2

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:
Fe +
hoc

Cu +

1
2
1
2

O2 + H2O = Fe2+ + 2OH

O2 + H2O = Cu2+ + 2OH

o
( EFe
2+

= 0,44 V)
Fe

o
( ECu
2+

= 0,34 V)
Cu

Trong trng hp vi nhng cp oxi ha kh c th in cc tiu chun dng hn th

in cc tiu chun ca oxi ( EOo 2
= 1,229 V), trng thi cn bng chng khng bn v
H2O

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

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

Da vo cc gi tr th in cc tiu chun bit tnh gin tip th in cc tiu

chun ca mt cp oxi ha kh kh xc nh.
o
V d: Tnh EFe
3+

Fe

o
khi bit EFe
2+

o
= 0,44 V v EFe
3+

Fe

Fe

th tiu chun ca cp Fe3+/Fe ta lp chu trnh sau:

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

3.6 Pin in (Pin Ganvani hoc mch in ha)

3.6.1 Pin in v cc phn ng xy ra trong pin
Mch in ha l mt h in ha gm t nht 2 in cc ghp li. Vic nghin cu v
pin in rt c ngha khoa hc trong vic gii thch n mn in ha.
Khi m t mt pin in c quy c nh sau:
Cc in cc c xp thnh mt hng, gia cc mt tip xc c quy c: mt gch
thng ng l gii hn gia pha rn v pha lng, hai gch thng l mt gii hn pha gia hai
cht lng tip xc (hoc l cu ni ca hai dung dch cht in li).
in cc t bn tri l cc m c gi l anot, in cc t bn phi l in cc
dng c gi l catot.
V d: Ghp hai in cc CuSO4/Cu v ZnSO4/Zn thnh pin in:
() Zn|ZnSO4 & Cu|CuSO4 (+)

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+

Trn anot ():

Cu2+ + 2e Cu

Trn catot (+):

;
;

EoZn2 +
o
ECu
2+

Phn ng chung ta c: Zn + Cu2+ Zn2+ + Cu

= 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)

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:
= 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

Vi phn ng tng qut xy ra trong pin l:

2 Red2 + 1 Ox1 U 2 Ox2 + 1 Red1
RT

= +

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

, khi hot cc cht phn

Re d 2

ng bng n v ( aOx1 , aOx2 , a Re d1 , a Re d2 = 1) th sc in ng ca pin bng sc in ng

tiu chun o. i vi pin Danien - Jacobi sc in ng tiu chun bng:
o
o = ECu
2+

Cu

EoZn2 +

= 0,337 ( 0,76) = 1,097 V

Zn

Nu aCu = aZn = 1 ; phng trnh (3.37) c dng:

= 1,097 +

0,059
2

lg

aCu2 +

(3.39)

a Zn2 +

Vy sc in ng ca pin in ph thuc vo hai gi tr l sc in ng tiu chun v

nng cc cht tham gia phn ng.

3.6.3 Phn loi pin in

Pin in c nhiu loi, song c th chia lm hai nhm chnh sau y:
1. Pin ho hc
Pin ho hc l mt h in ho gm hai in cc c tnh cht ho hc khc nhau ghp li,
n c phn chia thnh nhiu loi
a) Pin ho hc n gin
Pin ho hc n gin l h in ho gm hai in cc khc nhau nhng c chung cht
in li ghp li.
V d 1: Pin hiro v oxi, pin ny c s Pt, H2/H2O/Pt, O2.
Phn ng chung xy ra trong pin l:
H2 +

1
2

O2 + H2O U 2H+ + 2OH

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

= o + 0,0295 lg PH2 .PO1 2/ 2

(3.41)

V d 2: Pin tiu chun Weston

S pin: () Hg(25% Cd) / CdSO4(dd) / HgSO4 / Hg (+)
Trong pin dung dch CdSO4 c dng chung cho c hai in cc, cc m l in cc
loi 1, cc dng l in cc loi 2, phn ng xy ra trong pin l:
Cd + HgSO4 Cd2+ +2Hg + SO42
Gi tr sc in ng:
= o
= o

RT
2F
RT
F

lg aCd2 + .aSO2
4

lg a CdSO4

(3.42)

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

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

Pin nng l mt h in ho gm cc in cc ghp li to ra pin in, song nng

cht dn in loi 2 hoc cht dn in loi 1 khc nhau.
Loi pin ny tn ti trong cc loi n mn in ho, v d s n mn in ho do s
chnh lch nng oxi (n mn khe, n mn l).
Sau y l mt s v d:
V d 1: Pin nng
() Ag / AgNO3 // AgNO3 / Ag (+)
a1

a2

Gi thit a1(AgNO 3 ) < a2(AgNO 3 ).

Ti anot xy ra phn ng:
1e Ag+ (a1)

() 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).

V d 2: Pin nng oxi

Trong n mn in ho ho tan kim loi th oxi ng vai tr l cht nhn in t. Song s
c mt ca oxi ti cc vng khc nhau to ra cc in cc oxi c nng oxi khc nhau. Khi
khp kn to thnh pin nng oxi v lm tng tc n mn (xem chi tit trong phn n
mn kim loi trong iu kin c mt nng oxi khc nhau).

3.7 Phng php o sc in ng v ng dng

o sc in ng ca mt pin in cho php suy ra th in cc ca kim loi b n mn
trong mi trng cht in li. Trong mc nht nh, vic so snh th in cc n nh ca
kim loi trong mi trng n mn cho php suy on bn vng chng n mn ca vt liu.
V vy, vic o chnh xc gi tr th in cc c ngha nht nh.
o chnh xc sc in ng ca pin in ngi ta dng phng php b chnh. S
cu b chnh o sc in ng ca pin in c trnh by trn hnh 3.7 v trong :
iu kin o: cquy > x.
Nguyn tc o v tnh x: Di chuyn con chy K trn in tr AB sao cho khng c dng
i qua pin x v in k G ch s khng. Khi cu cn bng v ta c:

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

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.
Ta c:

cquy = w.

AB

AB

AK AK '

(b)

Kt hp hai cng thc (a) v (b) ta c:

x = w.

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

Ngy nay php o sc in ng ca pin in c ng dng rt rng ri trong vic ch

to cc thit b o: o pH, o th in cc, chun in th ca phng php in ho... Sau
y l mt s v d ng dng php o sc in ng ca pin in.
Nh bit, thng qua vic o nhit lng k xc nh c hiu ng nhit phn ng,
hoc nng lng G. Mt khc c th o sc in ng pin in tnh cc hm nhit ng.
Ta xt phn ng xy ra trong pin in Danien - Jacobi:
Cu2+ + Zn

Cu + Zn2+

(c)

tnh G phn ng ny bng cch o sc in ng ca pin Danien - Jacobi:

Ch to pin in theo hnh (3.6).
o sc in ng pin in 25oC thu c gi tr o .
Vy:

G = 2Fo = 2 96493. o

(3.44)

tnh H ca phn ng (c) ta p dng:

G = H TS
V:

= 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)

tnh H ca phn ng theo (3.48) trc ht phi xc nh h s nhit ca sc in

bng cch o sc in ng ph thuc nhit v t cc s liu th nghim suy
T p

ng

.
T p

ra

Phng trnh (3.48) cn c dng:

Qp

+ T

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

(Trong th in cc bc chn bng 0,2222 V).

(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.

4.2 C s s liu xy dng gin E - pH

Gin th in cc E - pH ca cc h kim loi (hoc oxit kim loi) tip xc vi mi
trng cht in li (dung mi nc) dng n gin hoc phc tp u da trn cc loi on
thng ng vi cc phn ng xy ra sau y trong h kho st (h n mn kim loi do mi
trng cht in li).

1.10.1 H oxi ho kh thun tu

Phn ng oxi ho kh khng c s tham gia ca ion H3+ O v ch trao i electron:

V d:

Ox + ne

Red

Fe3+ + 1e U

Fe2+

(4.1)

Trong trng hp ny gi tr th in cc E c tnh theo phng trnh Nernst ( 25oC)

v khng ph thuc pH.
E = Eo +

0,059
n

lg

aOx
aRed

(4.2)

51

i vi (4.1):

0,059
1

EFe3+ / Fe2+ = 0,77 +

hoc:

Khi t s

EFe3+ / Fe2+ = Eo +

aFe3+
aFe2+

lg

aFe3+
aFe2+

0,059
1

lg

aFe3+
aFe2+

(4.3)

= 1 th EFe3+ / Fe2+ = Eo = 0,77 V (SHE).

Khi biu din gi tr th ny vo pH trn gin E - pH (hnh 4.1a) ta c mt h

ng thng song song vi trc honh vi cc gi tr th khc nhau.

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).

1.10.2 H axit - baz thun tu

Phn ng xy ra trong h kho st ch c s trao i proton H3+ O v khng c s trao i
electron:
Mez+ +

z
2

H2O U

MeOz/2 + zH+

(4.4)

V d:
Cu2+ + H2O U

CuO + 2 H+

Hng s cn bng Kcb = K ca phn ng (4.4):

K=

azH+
z+

aMe

(4.5)

52

azH+ = K. aMez+
Vy:

pH =

lg

(4.6)

K.a Mez +

p dng phng trnh (4.6) tnh pH cho phn ng (4.5) ta c:

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 +

lg a Cu2 + , khi a Cu 2 + = 1; pH = 3,9

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.

1.10.3 H phn ng hn hp - C s trao i electron v c mt ion H3+ O tham gia

phn ng
Xt phn ng:
j Mj + mH+ + ze U /j Mj +

m
2

H2

(4.7)

V d:
Mn7+ + 8H+ + 5e U Mn5+ + 4H2O
trong :

(4.8)

j = /j = 1, j = Mn7+ v Mj = Mn5+

p dng phng trnh Nernst cho phn ng (4.7):

o

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

i vi phn ng (4.8) h s b = 0,059

m
n

( 25oC).

T phng trnh (4.9) gi tr th in cc phc thuc vo pH v trn th E - pH (hnh

4.1c) quan h c th hin bng h on thng c dc b = 0,059

m
z

4.3 Mt s gin E - pH (gin M. Pourbaix)

4.3.1 Gin ca nc tinh khit 25oC
Vic nghin cu gin E - pH ca nc rt c ngha i vi s n mn kim loi theo
c ch in ho.
Nc l mt cht in li rt yu:
2H2O U H3+O + OH

(4.10)

V vy nng H+ v OH rt nh, trong nc c mt lng kh O2 ho tan ( n gin

thay H 3+ O bng H+).

Cc phng trnh oxi ho kh c lin quan n H+, OH v H2O:

2H+ + 2e U H2

(4.11)

2H2O + 2e U H2 + 2OH

(4.12)

Phn ng (4.11) v (4.12) l cc phn ng in ho dng hn hp.

Phng trnh Nernst p dng cho phn ng (4.11) c dng:
o

25 C:

E2H+ /H

o
= E2H
+
+
/H
2

0,059
2

lg

a 2H+
PH2

Nu p sut ca H2 PH2 = 1 atm ta c:

E2H+ /H = 0,059 pH

(4.13)

Phng trnh ny cng ng cho phn ng (4.12).

Trn gin E - pH (xem hnh 4.2), phng trnh (4.13) c th hin trn on thng
OA..

54

Hnh 4.2
Gin E - pH i vi h H2O, H+, OH, O2

25oC vi PH = 1 atm, PO = 1atm

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+
hoc

2H2O

(4.14)

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 =

hoc:

EO2 / H2O = 1,228 V 0,059pH +

o
+
EO
2 / H2 O

lg a 4H+ . PO2

(4.16)

0,059

(4.17)

lg PO2

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.

4.3.2 Gin E - pH ca kim loi tip xc vi nc (Me - H2O)

4.3.2.1 Gin st - H2O (Fe - H2O)

St l thnh phn chnh ca cc hp kim thp c s dng rt rng ri trong cc ngnh

cng nghip ch to my cng nh trong cng nghip xy dng. Vic nghin cu nhng vn
c lin quan n st, thp c ngha nht nh i vi thc t.
thit lp gin th E - pH ca h Fe - H2O cn phi k n cc cu t tn ti trong
h: H2O, H+, OH, O2 v H2, Fe, Fe2+, Fe3+, HFeO2 , Fe(OH)3, Fe(OH)2 v cc phng trnh
phn ng c lin quan.
Cc phng trnh cn bng gia ion H+ v H2 c th hin trn cc phn ng (4.11),
(4.12), (4.13), s cn bng gia oxi v H2O th hin trn cc phng trnh tng ng (4.14),
(4.15) v (4.17).
i vi h Fe - H2O, cc phng trnh phn ng in cc ng vi cc phng trnh
Nernst tnh gi tr th in cc c trnh by trong bng sau y v chp nhn C Fe 2 + =

C Fe = C HFeO = 106M 25oC.

3+

Cc phn ng oxi ho kh thun tu:

o
= 0,44 V
Fe2+ + 2e U Fe vi EFe
2+
/ Fe
o
= 0,44 +
EFe
2+
/ Fe

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

Fe(OH)3 + 1e U H2O + HFeO2

EFe(OH)

(4.18)

(4.20)

= 0,50 V

Cc phn ng trao i proton thun tu:

Fe(OH)2 + 2H+ U Fe2+ + 2H2O pH = 9,64

(4.21)

Fe(OH)3 + 3H+ U Fe3+ + 3H2O pH = 3,62

(4.22)

HFeO2 + H

U Fe(OH)2

pH = 12,30 (4.23)

Cc phn ng hn hp trao i electron v proton:

56

Fe(OH)2 + 2H+ + 2e U Fe + 2H2O

(4.24)

o
E = EFe(OH)
+ 0, 059 lg C2H+
2 / Fe

(4.24a)

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.
o
+ 0, 059 lg CFe2 + , nng CFe2 + rt b.
E = EFe
2+
/ Fe

Vy:

E = 0,44 + 0, 059 lg TFe(OH)2 0, 059 lg C2OH

2

E = 0,44 + 0, 059 lg1,9.1015 0,059lg C2OH

2

E = 0,44 + 0, 059 lg1,9.1015 [0,059lg1014 0,059lg CH+ ]

2

E = 0,44 + 0, 059 lg1,9.1015 + 0,059.14 0,059pH

2

E = 0,44 0,434 + 0,826 0,059pH = 0,048 0,059pH (4.24b)

So snh (4.24b) vi (4.24a) rt ra:
o
= 0,048 V
EFe(OH)
2 / Fe

Vy (4.24a) ng vi phn ng (4.24) c dng:

E = 0,048 0,059pH
Vi tch s ho tan TFe(OH)3 = 7.1038 cho php tnh th in cc c lin quan n nng
Fe(OH)3.
Fe(OH)3 + 1e U Fe(OH)2 + OH

(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

Trong vng C st b n mn, vng P st b th ng. T gin th - pH ca h Fe - H2O

trnh by trn hnh 4.3 cho php rt ra mt s nhn xt sau:
D on kh nng b n mn v khng b n mn ca st trong mi trng nc. Tt
nhin khng em li mt thng tin g v tc ca cc phn ng xy ra.
Rt ra nguyn tc ca phng php in ho bo v chng n mn st trong mi trng
nc v c th l:

+ Dch chuyn th in cc st (thp) trong mi trng nc v pha m hn so vi th

n mn ca st th st i vo vng an ton khng b n mn. chnh l nguyn tc bo v
catot chng n mn kim loi (bng cch phn cc catot bng dng ngoi, hoc dng anot hi
sinh).
+ Dch chuyn th in cc ca st (thp) trong mi trng trng nc v pha dng so
vi th n mn (phn cc anot) s lm cho kim loi b th ng - gi l bo v anot.
+ iu chnh tng pH ca mi trng n mn a kim loi thp vo vng th ng lm
gim tc n mn kim loi.

Hnh 4.3
Gin th - pH i vi h Fe - H2O 25oC, P = 1 atm

4.3.2.2 Gin th E - pH ca nhm

Cc phn ng xy ra trong h nhm tip xc vi mi trng nc:

Al3+ + 3e U Al

(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)

Trong mi trng gn trung tnh Al b ho tan theo phn ng:

Al(OH)3 + 3e + 3H+ = Al + 3H2O

(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)

Th oxi ho kh tng ng 25oC vi C(OH) = 106M ta c:

4

E = 1,2 +

0,059
3

lg C( AlOH) 0,079pH
4

E = 1,32 0,079pH

(4.30a)

Phn ng trao i proton trong vng pH nh:

Al(OH)3 + 3H+ = Al3+ + 3H2O
1

lg C Al3 +

Vi gi tr

pH = 2,44

Vi

C Al3 + = 10 M th pH = 4,44 (4.31a)

(4.31)

Trong vng pH ln xy ra phn ng:

Al(OH)3 + OH = Al(OH)4
Vi

(4.32)

pH = 16,53 + lg C Al(OH)
4

Vi

C Al(OH) = 10 M th pH = 10,53

(4.32a)

Trn c s cc phn ng (4.28), (4.29), (4.30), (4.31), (4.32) v cc gi tr th in cc,

pH ng vi cc phng trnh: (4.28a), (4.29a), (4.30a), (4.31a), (4.32a), gin th E - pH
ca h Al - H2O c trnh by trn hnh (4.4).
Trn th ca hnh 4.4 cho thy rng: Vng (A) nm pha di ng abcd ng vi
min Al trng thi bn vng khng b n mn.
Vng (B) ng vi th dng hn 1,794 V trong khong pH t
nhm b n mn to ra ion Al3+.

0 4,4 kim loi

Vng (C) ng vi cc gi tr th dng hn so vi cc gi tr th trn on bc, kim loi

nhm trng thi bn vng nh lp ph Al(OH)3 (theo Gibbsite lp Al(OH)3 ny c dng
Al2O3.3H2O).

59

Vng (D) vi pH cao, vi cc gi tr th dng hn th trn on cd th Al b ho tan to

thnh Al(OH)4 (hoc AlO2 .2H2O).

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

Kim loi km c dng ph bin lm lp m km trn nn st nhm bo v st khi s

n mn ca mi trng nc gy ra. Km b n mn trong mi trng nc trong khong pH
t 0 8.
iu kin cn bng xy ra phn ng sau:
Zn2+ + 2e U Zn

(4.33)

Th cn bng ng vi phn ng (4.33) 25oC bng:

E = 0,76 +

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)

Trong vng kim thp xy ra phn ng sau:

Zn(OH2) + 2H+ + 2e U Zn + 2H2O

(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

E ZnO / Zn = E 0,118pH + 0,0295lg C ZnO

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)

vi hng s Kcb = 7.58.1010

lgKcb = lg7,58.1010 = 2lg CH+ lg C Zn 2 +

Vy
hoc

lgKcb = 2pH + lg C Zn 2 +

10,88 = 2pH + (6)

Vy

pH = 8,439

(4.36a)

Khi pH tng th Zn(OH)2 b ho tan thnh dng ion Zincat.

Zn(OH)2 = ZnO22 + 2H+
ti gi tr pH = 10,88

(4.37)
(4.37a)

T nhng phn ng (4.33), (4.34), (4.35), (4.36), (4.37) ng vi cc gi tr th v pH theo

cc phng trnh (4.33a), (4.34a), (4.35a), (4.36a), (4.37a) ta v c gin th E - pH i
vi kim loi km c trnh by trn hnh (4.5).
Trn hnh 4.5 cho thy: Vng A km khng b n mn. Trong khong ab ng vi th
dng hn nm pha trn ab th km b ho tan thnh ion Zn2+. Trong vng C trn b mt km
tn ti lp Zn(OH)2 t tan to mng th ng km hm s ho tan ca km. Khi pH tng trong
khong cd, ti vng D hiroxit km b ho tan to thnh ion Zincat. V vy trong vng pH >
10,88 vi cc gi tr th dng hn cc gi tr th trn ng cd th kim loi k b n mn to
ra ion zincat ZnO22 .

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)

ng vi trng thi cn bng c th cn bng Ecb, phn ng t xy ra v khng c dng

ngoi i qua.
V d 2: Kim loi platin nhng trong dung dch cha h oxi ho kh Fe3+, Fe2+. Phn ng
in cc l:

Fe3+ + 1e U Fe2+

(5.2)

i khi th cn bng Ecb ca cc phn ng (5.1), (5.2) cn c gi l th thun nghch

hoc l th dng.
Khi c s phn cc in cc bng dng ngoi hoc bng khp kn mch in, th in cc Ei
b dch ra khi th cn bng Ecb, lch ny c gi l s phn cc in cc v thng c k
hiu l E hoc (qu th).
Vy:

E = = Ei Ecb

(5.3)

Nu lch > 0 so vi th cn bng Ecb gi l phn cc anot v ngc li l <

0 - s phn cc catot.

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

V km theo phn ng:

1
2

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)

Trong iu kin cn bng, trn mt gii hn pha tn ti hai h oxi ho kh ng vi cc

phn ng (5.4a) v (5.5a).
Khi c s phn cc trn mt gii hn pha xy ra ng thi hai phn ng (5.4) v (5.5)
theo chiu thun v c phn ng tng cng:
Cu +

1
2

O2 + 2H + Cu2+ + H2O

(5.6)

Trong trng hp ny kim loi ng b ho tan, ngha l ng b n mn km theo s tiu

th oxi v khng c dng ngoi i qua.

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).

5.2 Hin tng n mn in ho v cc giai on ca qu trnh n mn

in ho
n mn in ho xy ra khi kim loi tip xc vi dung dch cht in li l s ph hu kim
loi xy ra trn mt gii hn hai pha: kim loi v dung dch cht in li, khi kim loi b ho
tan xy ra trn vng anot v km theo phn ng gii phng hiro hoc tiu th oxi xy ra trn
vng catot ng thi sinh ra dng in. Qu trnh n mn in ho xy ra tng t s hot ng
ca mt pin in b khp kn mch (xem hnh 5.2).

64

Hnh 5.2
S n mn in ho ca kim loi t trong dung dch cht in li

Trn b mt kim loi c tn ti cc vng anot v vng catot l do s chnh lch v th

trn b mt gii hn pha. C rt nhiu l do gii thch s chnh lch th ny. V d do c
mt ph gia hp kim, do s lch mng cc tinh th kim loi v.v...
gii thch qu trnh n mn in ho ca mt kim loi nhng trong dung dch in li,
ta xt trng hp n gin c th hin trn hnh 5.2. Trn b mt kim loi c hai vng anot
v vng catot. Gi tr th in cc ti vng anot m hn so vi th in cc vng catot. H
ny c khp kn mch v xy ra cc phn ng sau:
Vng anot xy ra qu trnh oxi ho tc l kim loi b ho tan:
Me Ze MeZ+

(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)

v khi s n mn kim loi km theo s gii phng hiro.

Nu trong mi trng n mn c mt ion H+ v oxi th xy ra phn ng tiu th
oxi.
Z
4

O2 + Ze + ZH+

Z
2

H2O

(5.9)

Vy s n mn km theo s tiu th oxi c mt trong dung dch.

Qu trnh n mn ho tan kim loi cng nh qu trnh xy ra trn catot l gii phng
hiro hoc tiu th oxi thng bao gm cc giai on (xem hnh 5.2) sau y:
Vng anot

65

a) Giai on ho tan kim loi li electron trn in cc.

b) Giai on chuyn sn phm ca s oxi ho (chuyn cc ion t b mt kim loi vo th
tch dung dch).
Vng catot

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.

5.3 Phng trnh ng hc in ho

5.3.1 Phng trnh ng hc in ho xy ra trn in cc n
Trong trng hp tng qut, trn b mt gii hn pha ca in cc xy ra phn ng in
ho.
v

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

trong : I- cng dng in i qua bnh in phn (qua in cc);

dq - bin thin ca in lng;

66

dt - bin thin ca thi gian (pht, gi ...);

v - l tc phn ng ho hc (mol.m2.s1);
Z - s electron trao i trong phn ng in ho;
F - s Faraday (F = 96493 C).
Tc phn ng thun ca phn ng (5.10) gi l phn ng catot
v

Ic = ZFvc

(5.11a)

Tc phn ng nghch ca phn ng (5.10) gi l phn ng anot

v

Ia = ZFva

(5.11b)

Trong in ho thng dng i lng mt dng in i (A/cm2) thay cho cng

dng I (A) v bng:
i=

I
S

( A cm2 , A m2 ) trong S l in tch in cc (cm , m ).

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

Trong G*c v G*a gi l nng lng hot ng ho in ho i vi phn ng catot

v anot, n quan h cht ch vi s tn ti ca lp in kp trn mt gii hn pha ca in
cc, ngha l vi th in cc.
Trn hnh 5.3 trnh by s quan h gia G*c , G*a v th in cc. G o - nng lng
hot ng ho ng vi trng thi cn bng ca phn ng (5.10).
Khi c s phn cc dng vi th in cc E th cng tch in A bng:
A = ZFE
Khi qu trnh anot xy ra phn ng Red Ox + Ze. V d kim loi chuyn thnh ion
kim loi i vo dung dch s d dng hn vi nng lng hot ng ho G*a v bng:
o

G*a = G ZFE

(5.13)

i vi qu trnh catot, s chuyn ho cc phn t Ox thnh Red t dung dch n in

cc s kh khn hn (v d chuyn ion kim loi thnh kim loi MeZ+ + Ze Me).
Vi nng lng hot ng ho bng G*c :
G*c = G o + (1 )ZFE = G o + ZFE

(5.14)

Cc h s v gi l h s chuyn in v + = 1 . Kt hp cc phng trnh

(5.12a), (5.12b), (5.13) v (5.14) ta c:
G o ZFE

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

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

RT

(5.18)

ZFEcb

RT

(5.19)

ia = ZFKa. CoRe d .exp

o
ic = ZFKc. COx
.exp

Ti cn bng tc cc phn ng ia = ic = io; io gi l dng trao i.

ZFEcb
ZFEcb
o
= ZFKC. COx .exp
(5.20)
RT
RT

io = ZFKa. CoRe d .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

= 1 th Ecb = Eocb gi l th in cc tiu chun.

Kt hp cc phng trnh (5.20) v (5.22) rt ra:

1

o
o
o
= ZFK so .COx
.CRe
io = ZFK1a .K c .CoRe d .COx
d

(5.24)

trong K so = K1a .K c , khi cn bng Kc = Ka, mt khc gi tr K so khng ph thuc vo

th in cc.
Vy dng trao i io khng hon ton l c trng duy nht cho ng hc ca phn ng
in ho m cn ph thuc vo nng cht phn ng.
t i oo l mt dng trao i tiu chun:
i oo = ZFK so

Vy

(5.25)

o
o1
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

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)

Quy c dng catot ic c du m v khi :

i = ia ic

Kt hp vi cc phng trnh (5.16) v (5.17) ta c:

ZFEi
ZFEi
i = ZFK a .CRe d .exp
ZFK c .COx .exp
(5.29)
RT
RT

Gi tr th Ei khc th cn bng Ecb.

Nu em chia phng trnh (5.29) cho (5.20) ta c:
i
io

CRe d
CoRe d

ZF(Ei Ecb ) COx

ZF(Ei Ecb )
exp
o .exp

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)

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.
o
=
Nu giai on khuch tn cht phn ng din ra nhanh ngha l CoRe d = CRed v COx
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

RT
RT

(5.32)

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
.exp
.exp

o
o
RT CFe3 +
RT
CFe2 +

(5.33)

trong CFe2 + , CFe3 + l nng cc cht kh v cht oxi ho trn b mt in cc khi c

o
o
dng i i qua h in ho, cn CFe
l nng trong dung dch cht in li cng l
2 + v C
Fe3 +
nng lc cn bng.
o
o
Vy khi CFe2 + = CFe
= CFe
2 + v C
3 + th phng trnh (5.33) s c dng ca phng
Fe3 +
trnh (5.32).

Trn hnh 5.4 trnh by dng ng phn cc vi phng trnh (5.32).

70

Trong min phn cc ln, ngha l qu th c gi tr ln th phng trnh (5.32) s c

cc dng sau:
Nu phn cc anot ln th dng ia >> ic v dng chung i xp x bng dng anot ia v khi
phng trnh (5.32) c dng.
a
ZFa
i = ia = i o .exp
= i o .exp
RT
a

(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

>> 1 th quan h i v c dng hm m (ng ia trn hnh 5.4).

Mt cch tng t khi c s phn cc catot ln; ngha l i c >> ia th mt cch gn ng

ta c:
c
ZFc
i = i c = i o .exp
= i o .exp
RT

(trong : c =

RT
ZF

) v

c
c

(5.37)

<< 1 .

T (5.37) c th rt ra: c = c lgic c lnio

hoc

c = Ac + Bc lgic

(5.38)

71

trong :

A c = c ln i o v Bc = 2,303c .

Cc phng trnh (5.36) v (5.38) c gi l cc phng trnh Tafel v c trnh by

trn hnh(5.5).

Hnh 5.5
S ph thuc ca vo lgi
(a) on thng Tafel anot; (b) on thng Tafel catot

Bng cc s liu th nghim o i (A/m2) theo s bin i ca th hoc ngc li c th v

c cc on thng Tafel. Bng php ngoi suy cc on thng catot v anot cho php xc
nh c dng trao i io ca h oxi ho kh kho st trn mt loi vt liu in cc nht
nh (xem hnh 5.5). ng vi dng io xc nh d dng suy ra th cn bng thun nghch Ecb.
Nu s phn cc in cc rt nh, ngha l qu th <<

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)

Nh vy, vi s phn cc b, quan h gia th v mt dng ca ng phn cc tun

theo nh lut m. S ph thuc ny l tuyn tnh v ng vi on thng OO trn hnh (5.4).
Bng cc s liu thc nghim, trn th th ph thuc vo mt dng i (A/m2) ti
min qu th nh cho php xc nh trc tip RP v da vo (5.41) suy ra gi tr mt dng
trao i io.
Mt khc, da vo dng ng cong phn cc i = f() (xem hnh 5.4) hoc = f(i) cho
php phn loi h in cc phn cc l tng v h khng phn cc.
Mt h in ho c gi l phn cc l tng nu trong khong th phn cc gn th cn
bng Ecb c gi tr dng trao i rt nh, ngha l

d
di

v cng ln (xem hnh 5.6). V ngc li,

72

h in ho khng phn cc nu khi phn cc ti vng th gn th cn bng Ecb c

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

; a2b2 - H khng phn cc

d
di

5.3.2 S chuyn vt cht

Thng thng, khi c s phn cc ln (anot hoc catot), phn ng trao i electron trn
mt gii hn pha ca in cc din ra kh nhanh v lm gim nng b mt cht phn ng
ng k. Do c s chnh lch nng cht phn ng (cht kh hoc cht oxi ho) ti vng
phn ng v trong th tch dung dch. S chnh lch ny l nguyn nhn sinh ra s phn cc
nng v cn gi l qu th nng . Tc chuyn vt cht, ngha l chuyn cht phn
ng t trong th tch dung dch n vng phn ng trn mt gii hn pha ca in cc hoc
chuyn sn phm vo dung dch cht in li c quan h cht ch v nh hng n qu th
nng . Sau y s trnh by cc vn c lin quan nhm thit lp phng trnh ng hc
chuyn cht v thng gi l ng hc khuch tn trong phm vi in ho.
5.3.2.1 Phng trnh Fick 1 p dng cho s khuch tn cht in li

Trong qu trnh xy ra phn ng in ho trn b mt gii hn pha ca in cc m giai

on chuyn cht phn ng ngha l chuyn cc ion n b mt in cc hoc chuyn sn
phm t b mt in cc vo dung dch l giai on chm nht so vi cc giai on khc th
ng hc ca phn ng c khng ch bi s chuyn cht. S chuyn cht c th c thc
hin bng cc cch sau:
S chuyn cht lng bng dng i lu l do mt lc tc dng c hc no ; do s
chnh lch v t trng cht lng gia cc vng khc nhau, do s chnh lch v nhit v.v...
Song cn lu rng cht lng nm st b mt in cc khng chu chuyn ng i lu m

73

ch c s khuch tn. Hin tng khuch tn vt cht xy ra l do s chnh lch v nng

cht phn ng ti b mt in cc v trong th tch dung dch.
Theo nh lut Fick 1, khi c s chnh lch nng ca mt cu t i no ti vng st
b mt in cc v trong th tch dung dch th dng cht lng Ni c di chuyn theo phng
thng gc n b mt in cc c quan h vi s bin thin nng Ci theo to X c th
hin bng phng trnh sau:
dC
N i = Di i
dx x =0

O2).

(5.42)

trong Di l h s khuch tn ca cu t i (i: l ion hoc l mt cht trung tnh, v d

Nu gi Coi l nng cu t i trong th tch dung dch v CSi l nng cu t i ti gn

st b mt in cc, l chiu dng lp khuch tn (xem hnh 5.7); phng trnh (5.42) c
dng sau:
N i = Di

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

Chiu dy ca lp khuch tn cn c gi l dy khuch tn Nernst. dy ca

lp khuch tn trong thc t l l thng ln hn , ngha l l > . Nu hiu s gia l v cng
ln th s chuyn cht do i lu cng tng ln. Vy c th dng dy phn nh ranh
gii gia chuyn ng khuch tn v i lu.
Gia dng cht lng Ni v mt dng iln c quan h vi nhau theo phng trnh:
i = ZFNi
hoc:

i = ZFDi

(5.44)
Coo CSi

(quy c du + i vi dng anot v du i vi dng catot).

(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)

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:
i = ZFDi

Cibh Coi

(5.47)

v khi Cibh >> Cio ta c dng gii hn id bng:

i = ZFDi

Cibh

(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.
5.3.2.2 Phng trnh ng hc khuch tn - quan h gia qu th nng v mt
dng
+

Trong h in ho gm kim loi ng nhng vo dung dch long ng sunfat c mt ion

H.
Khi phn cc catot trn in cc xy ra phn ng:
Cu2+ + 2e Cu

Nu phn cc catot rt nh th nng ion Cu2+ trn b mt in cc CsCu2 + gn bng

o
nng ion Cu2+ trong th tch dung dch CCu
2 + , khi giai on trao i in tch khng ch
o
ng hc ca ton b qu trnh. Gi tr th cn bng ng vi nng CCu
2 + c tnh bng
phng trnh:

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 +

gi l qu th nng hoc qu th khuch tn .

75

c = Ei

Cu2 +

Cu

ECu2 +

=
Cu

RT
2F

ln

CsCu2 +
o
CCu
2+

(5.51)

Kt hp cc phng trnh (5.45) (5.46) v (5.51) p dng cho ion Cu2+ ta c:

CsCu2 +
o
CCu
2+

=1

(5.52)

id

T cc phng trnh (5.52) v (5.51) ta c:

c =

hoc

ln 1
2F
id

RT

(5.53)

2F

i = id 1 exp
c
RT

(5.54)

p dng phng trnh (5.54) cho mt ion bt k c s electron trao i bng Z ta c:

ZF

i = id 1 exp
c
RT

(5.55)

Trn hnh 5.8 trnh by s bin i mt dng i theo s phn cc catot.

Hnh 5.8
S ph thuc ca mt dng i(A/m2) v phn cc catot (v)

ng cong trn hnh 5.8 c chia lm ba min

Min 1 ng vi gi tr phn cc catot rt nh <<

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

Vy quan h gia i v c trong min qu th c b l tuyn tnh.

Min 3 ng vi s phn cc catot ln c >>

RT
F

i = id

v phng trnh (5.55) c dng:

(5.59)

on AB trn hnh (5.8) ng vi vng ng hc khuch tn, gi tr i = id l hng s v

khng ph thuc vo s dch chuyn th v pha m.
Min 2 c gi l min chuyn tip ca hai loi ng hc, ng hc trao i electron v
ng hc khuch tn.
Theo phng trnh (5.46), mt dng gii hn id t l thun vi nng cht phn ng
trong dung dch Co. Khi nng ny tng th dng gii hn id tng. V d s n mn kim loi
ca st trong mi trng phn trung tnh tng ln, ngha l id tng khi nng oxi trong dung
dch tng.
Mt cch tng t, khi ha tan anot mt kim loi no trong dung dch cht in li, sn
phm ho tan tch t trn b mt in cc, khi nng b mt Cs rt ln so vi nng
trong dung dch Co. Do s chnh lch nng cng sinh ra s phn cc nng ng vi qu
trnh khuch tn sn phm phn ng vo dung dch. Dng khuch tn id cng c tnh mt
cch tng t theo cng thc (5.46).

5.3.3 Phng trnh ng hc ca qu trnh b khng ch hn hp

Giai on chm nht khng ch ng hc in ho ca mt phn ng in ho xy ra trn
b mt gii hn pha ty thuc vo mt dng hoc gi tr th phn cc c p t cho h
in ho kho st.
V d phn ng catot tch kim loi ng t ion ng Cu2+ trong dung dch. Vi mt
dng catot b, s kt ta in ho theo phn ng Cu2+ + 2e Cu b khng ch bi s chuyn
in tch; nhng khi tng mt dng i kh cao th ng hc ca ton b qu trnh kt ta
trn li b khng ch bi s chuyn cht - ng hc khuch tn.
T phng trnh (5.31) v (5.37) p dng cho qu trnh catot kt ta ng t ion Cu2+
trong dung dch ta c mt dng ic c tnh theo phng trnh:
i c = i o

CsCu2 +
o
CCu
2+

exp c
c

(5.60)

Kt hp phng trnh (5.60) v (5.52) ta c:

i
i c = i o 1 c
id

Sau khi bin i ta c:

c
exp

(5.61)

77

i o exp c
c
ic =
i

1 o exp c
id
c

(5.62)

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
i
ic
c
= d
id
i

1 o exp c
id
c

Nu c c gi tr rt ln th

ic
id

(5.63)

1 , ngha l ic = id v khi ng hc ca qu trnh c

khng ch bi s khuch tn.

5.4 n mn in ho - h in cc phc tp xy ra nhiu phn ng

n mn kim loi theo c ch in ho xy ra trong mi trng cht in li vi dung mi
nc gm nhiu phn ng in ho xy ra cng mt lc trn mt gii hn pha kim loi - dung
dch cht in li.
Ti anot xy ra phn ng ha tan kim loi thnh ion kim loi i vo dung dch v km
theo cc phn ng catot - kh cc cu t oxi ho c mt trong dung dch (H+, O2...).
Do tnh cht bt ng th trn b mt kim loi cho nn trn b mt kim loi c rt nhiu
pin in ho nh v gi l vi pin cho nn khng cn c s phn chia r rng vng catot v
anot. S ho tan kim loi ti v tr anot ng thi chuyn electron cho catot bn cnh thc
hin phn ng kh. S chuyn electron ny xy ra l nh s dn in ca kim loi.
Trn c s ca m hnh ny Wagner v Trand a ra l thuyt in th hn hp ca s
n mn in ho cho php xc nh th n mn Em cng nh tc n mn thng qua dng
n mn im.
Sau y chng ta s kho st mt s trng hp n mn in ho trn c s l thuyt in
th hn hp.

5.4.1 S n mn kim loi ng u trong mi trng axit

Xt trng hp nhng st sch vo mi trng axit khng cha oxi.
Qu trnh n mn st sch c th xy ra cc phn ng oxi ho kh sau y:
iFe

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)

Nu c mt oxi s c cc phn ng:

O2

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)

Trong mi trng axit st b ho tan gn lin vi hai phn ng oxi ho kh ch yu ng

vi cc phn ng (5.64) v (5.65).
Qu trnh n mn in ho ca st trong mi trng axit xy ra tng t s hot ng ca
mt pin in khp kn mch, ngha l ti v tr st b ho tan cho ion st Fe2+ s ng vai tr l
Fe
anot v cn bng dch chuyn vi iFe
a >> i c :
iFe

c
ZZ
XZ Fe
Fe2+ + 2e YZZZ
iFe

(5.69)

Ti v tr trn b mt kim loi st trong mi trng axit ng vai tr l catot s xy ra

+
H+
phn ng ch yu l gii phng hiro vi iH
c >> i a :
iH

c
2H + 2e ZZZZ
YZ
ZX H2
H+

(5.70)

ia

Cng hai phn ng (5.69) v (5.70) ta c phn ng chung sau:

Fe + 2H+ Fe2+ + H2

(5.71)

Khi phn ng (5.71) xy ra t trng thi n nh th cc qu trnh catot v tng cc qu

trnh anot ca cc h oxi ho khi xy ra trn b mt gii hn ca st v dung dch axit bng
nhau:
+

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)

(im = dng n mn; i - dng n nh)

ng vi dng n mn im c gi tr th hn hp hoc cn gi l th n mn, Em, n nm
trong khong gia cc gi tr th cn bng ca phn ng (5.64) v (5.65); ngha l h oxi ho
+
2+
kh 2H H b phn cc catot v h oxi ho kh Fe Fe b phn cc anot. Trn hnh 5.9
2
trnh by ng cong phn cc i - E ca cc h phn ng oxi ho kh (5.64), (5.65) v h oxi
ho kh hn hp theo (5.71).

79

Trn hnh 5.9 ch ra rng ti th n mn Em ng vi gi tr dng n mn |im| = | iFe

a | =
+

| iH
c |; khi phng trnh (5.71) ng vi trng thi n nh.

Khc vi dng io ca h oxi ho kh n, dng n mn im c yu t ng hc.

2+
Nu xem Em l th phn cc i vi h Fe Fe v ng vi dng n mn bng:

( )

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

Trong trng hp khi c s phn cc ca dng ngoi ng vi th Ei Em (Ei Em > 0

phn cc anot v Ei Em < 0 phn cc catot) th phng trnh quan h gia mt dng i
ng vi th phn cc Ei v dng n mn im c th hin bng phng trnh sau y:
i vi s phn cc anot Ei Em > 0 th iFe
a c dng:
ZF
ZF
Fe
Fe
Fe
Fe
iFe
Ei Ecb = i o exp
( Ei Eam ) + Eam Ecb
a = i o exp
RT
RT

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)

Mt cch tng t, i vi qu trnh catot gii phng hiro ta c phng trnh:

+
ZF
iH
(Ei Em)
a = im.exp
RT

(5.78)

Nu gi i l dng chung ca qu trnh st b n mn trong mi trng axit vi th phn

H+
cc Ei v bng i = iFe
a + | i c |; t Ei Em = , ta c:

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

th phng trnh (5.79)

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

, phng trnh (5.79) c dng sau y:

i vi s phn cc anot l i = ia:

ZF
a
RT

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

-0,40 -0,60 -0,80 -

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);

3. H hn hp ca (1) v (2) (suy ra Em v im)

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

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.

(5.87)

82

T (5.87) tnh c tc n mn (g/S.t) =

m
S.t

, trong S l din tch mu (cm2,

dm2, m2) v t l thi gian din ra qu trnh n mn (gi, ngy m, thng, nm).

5.4.2 Mt s yu nh hng n dng n mn im

5.4.2.1 nh hng ca mt dng trao i io

Khc vi mt dng trao i io ca h oxi ho kh n, dng n mn im khng nhng

ph thuc vo hiu in th cn bng ca cc h n m cn ph thuc vo dng ca ng
cong phn cc anot v catot ca cc h n, ngha l ph thuc vo mt dng trao i io
ca h n. lm sng t diu ny, ta xt v d sau:
Khi nhng 2 kim loi sch st v km vo mi trng axit khng cha oxi s xy ra s n
mn in ho ca st v km.
Gi thit nng ion st bng CFe2 + = 106M v CZn2+ = 106 M v CH+ = 1M. T suy
ra cc gi tr thun nghch ca cc h oxi ho kh 25oC bng:
Fe2 +

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

Qu trnh n mn st v km trong mi trng axit u km theo s thot kh hiro. V

nguyn tc, s ho tan km vi tc rt ln so vi tc n mn st v hiu in th gia
hai in cc hiro v km rt ln so vi hiro v st. Trong thc t dng n mn ca km
2H+

trong axit c gi tr nh v dng trao i i o

(xem hnh 5.11).

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)

1-1: H 2H+ + 2e U H2 trn km;

2-2: H 2H+ + 2e U H2 trn km;

3-3: H Fe2+ + 2e U Fe;

4-4: H Zn2+ + 2e U Zn

T hnh 5.10 cho thy gi tr n mn ph thuc vo mt dng trao i io ca cc h oxi

ho kh kho st.
Fe
Gi thit dng trao i ca hiro trn Zn v trn st bng nhau i Zn
o.H2 = i o.H2 th dng n

mn ca km ng vi im P rt ln so vi dng n mn ca st (xem hnh 5.10):

( 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

5.4.2.2 nh hng ca s b sung cht oxi ho

S c mt ca cht oxi ho c th oxi ho kh dng hn so vi th oxi ho kh ca h

2H + 2e U H2 s lm tng tc n mn kim loi. V d s n mn kim loi Me trong mi
trng axit (H2SO4) khng c mt oxi v c thm ion Fe3+.
+

Me Ze Me2+

Phn ng anot:
Phn ng catot:

2H+ + Ze

Z
2

2
H2 E H
tn = 0,00 V

84

3+

ZFe3+ + Ze ZFe2+ EFe

tn

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:

i c H+ H + i c Fe3 + Fe2 + > i c H+ H

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.

5.5 Gin Evans xc nh tc n mn kim loi

Gin xc nh tc n mn in ho c xy dng da trn cc ng phn cc i =
f(E) (xem hnh 5.12a) ring ca tng h oxi ho kh n ng vi cc qu trnh chim u th
c ghp li thnh ng phn cc chung cho ton b qu trnh n mn. Trong qu trnh
anot l kim loi b ho tan v km theo qu trnh catot vi s gii phng hiro hoc tiu th
oxi.
Gin Evans c xy dng da trn 2 nhnh ca cc ng phn cc catot v anot
ng vi s hot ng ca mt pin n mn tng t mt pin in khp kn mch (xem hnh
5.12b).

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

v Ecb Re d ng vi gi tr dng n mn im=|ic|

85

Nu khng tnh n du ca dng in v ch tnh n gi tr tuyt i v sau khi v

ng O 1 A 1 i xng vi O1A1 qua trc O1O2 v ct O2C ti im O3; khi ta c on
thng OO3 bng ic = ia = im. Tam gic O1O2O3 t hnh 5.12a di chuyn sang hnh 5.12b
gi l gin Evans v n mn kim loi. Trn hnh 5.12b ta c:
Me2 +

Ecb

Me

Ox

< Em < Ecb Re d

on thng O1O3 - ng phn cc anot.

on thng O2O3 - ng phn cc catot.
on thng O3O4 ng vi ln dng n mn im = ia = ic.
Theo hnh 5.12b, khi mt pin n mn cc b hot ng, dng in ban u ca pin c
tnh theo cng thc:
Im =

Eccb Eacb

(5.88)

(khi tnh cho ton b din tch ca in cc c th thay th im = Im).

trong : Eccb , Eacb - th in cc ca catot v anot trng thi cn bng.
R - in tr ton mch.
Khi khp kn mch, dng in i qua h thng pin n mn, cc in cc b phn cc catot
v anot ng vi cc gi tr in th Eci v Eai . Vy:
i vi phn cc catot:
c
Eci = Ecb
+ E c

( Ec < 0 )

(5.89)

( Ea > 0 )

(5.90)

i vi phn cc anot:
Eai = Eacb + Ea

V Ec v Ea c gi tr nh nn quan h gia ic, ia v Ec, Ea l tuyn tnh.

Ta c Ec = RPc i c trong RPc - in tr phn cc catot.

(5.91)

Ea = RPa ia trong RPa - in tr phn cc anot.

Kt hp cc phng trnh: (5.88), (5.89), (5.90) v (5.91) ta c:

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

Eccb RPC .iam Eacb RPa .iam

hoc

im =

hoc

im ( R + RPc + RPa ) = Eccb Eacb

Ta c:

im =

(5.95)

Eccb Eacb

(5.96)

R + RPc + R Pa

Vy tc n mn im ca kim loi thay i theo phn cc RPc ; RPa v in tr R ca

mch. in tr R gm hai thnh phn: in tr ca mi trng n mn gia hai in cc c
gi l in tr ni Rin v in tr ca dy dn loi 1 ni 2 in cc gi l in tr ngoi Rex
(nghch o dn in ca kim loi b n mn). S mch in tng ng ca pin n
mn do hai kim loi khc nhau c trnh by trn hnh 5.13.

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 :

1. Cc m - kim loi b n mn;

2. Cc dng, ti xy ra phn ng kh cht oxi ho (H+, O2
hoc ion c tnh oxi ho cao);
Rin v Rex - in tr ni v in tr ngoi;
RPc ; R Pa - in tr phn cc catot v anot;
Eacb ,Eccb - Th in cc cn bng ca anot v catot;
Eai ;Eci - Th in cc ca anot v catot khi c dng im i qua pin

(cn gi l th phn cc anot v catot).

Kt hp hai phng trnh (5.95) v (5.96) ta c:
im =

Eccb Eacb
R Pc + RPa + R in + Rex

(5.97)

Trn hnh 5.14 trnh by gin Evans vi mt dng n mn im ph thuc vo cc gi

tr th in cc ca catot v anot trng thi cn bng v in tr R ca pin n mn.

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)

a) Tng phn cc anot; b) Tng phn cc catot

Khi phn cc anot cng ln E1a > Ea2 th dng n mn cng gim i1am < i2am .
Qu trnh n mn b khng ch bi phn ng anot, v d kim loi ch nhng trong dung
dch H2SO4. Vy phn trm n mn in ha b khng ch anot Ha% c tnh theo phng
trnh sau:
Ha% =

Ea
Ea + Ec + iR

.100%

(5.98)

2) S hot ng ca pin n mn kim loi b khng ch bi phn ng catot (xem hnh

5.15b) nu s phn cc catot E1c > E1a ; khi tng phn cc catot E2c > E1c th dng n mn
b gim i2am < i1am ng thi th n mn Em dch v pha th cn bng anot Eacb . V d kim
loi km b n mn trong mi trng H2SO4. Mt khc, nu trong dung dch c mt cht c
ch lm tng phn cc catot gim tc n mn th c gi l cht c ch catot.
Vy phn trm n mn in ho b khng ch bi qu trnh catot Hc% c tnh theo
cng thc sau:
Hc% =

Ec
Ea + Ec + iR

.100%

(5.99)

3) Nu in tr ni ca mi trng n mn trong pin n mn rt ln R th dng n

mn im rt nh, s phn cc catot v anot rt nh, khi s n mn b khng ch bi in tr
HR% c tnh theo cng thc:
HR% =

iR
Ea + Ec + iR

.100%

(5.100)

89

4) n mn phn cc anot v catot v in tr ca pin n mn R khng khc nhau qu

nhiu th s n mn in ho b khng ch ng thi bi phn cc catot, anot, in tr v gi
l khng ch hn hp (xem hnh 5.14).

5.6 n mn in ho ca kim loi bi mi trng cht in li c mt oxi

Nh bit, trong mi trng axit, s n mn kim loi b khng ch bi phn ng catot
kh ion H+ to ra kh H2. Nu trong mi trng n mn gn trung tnh c mt oxi ho tan (oxi
t khng kh ho tan vo dung dch) th tc n mn kim loi b khng ch bi giai on
khuch tn oxi.
V nguyn tc, qu trnh n mn in ho xy ra gm hai qu trnh: Ti anot xy ra phn
ng ho tan kim loi Me.
Me Ze MeZ+
v ng thi trn catot xy ra phn ng kh oxi ho tan trong dung dch:
Trong mi trng axit long:
Trong mi trng kim:

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)

Th in cc ng vi (5.102) trng thi thun nghch bng:

RT

Ecb(O2 ) = Eo +

4F

ln

PO2
a4OH

(5.103)

Nu pH = 7 v t = 25oC, p sut ring ca oxi trong nc bng PO2 = 0,2 atm.

Ecb(O2 ) = 0,81 V NHE

Vy trong mi trng n mn c cha oxi v phn ng catot kh oxi chim u th th cc

kim loi c th in cc dng hn th tiu chun hiro v nh hn gi tr +0,81 V s b n
mn in ho tiu th oxi.
V d khi nhng kim loi Cu vo dung dch H2SO4 long cha oxi, khi ng ng vai
o
tr l anot, xy ra phn ng (gi thit ECu
= +0,34 V):
2+
Cu

2+

Cu 2e Cu
Trn catot xy ra phn ng:
1
2

O2 + 2e + H2O 2OH

90

v phn ng chung:

Cu +

1
2

O2 + H2O Cu2+ +2OH

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:
iC(O2 ) =

trong : iOo 2

o
i O
2

CSO2
o
CO
2

4 c
exp O

2
RT

(5.104)

- dng trao i ca phn ng (5.102).

CSO2

- nng oxi trn b mt st in cc.

o
CO
2

- nng oxi trong th tch dung dch.

Khi c s phn cc catot ln c

RT
ZF

th nng oxi trn b mt rt nh CSO2 0 v

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)

trong DO2 l h s khuch tn ca oxi, l chiu dy lp khuch tn.

Khi CSO2 0 th (5.105) c dng:
iC(O2 ) = id = 4FDO2

o
CO
2

(5.106)

trong id gi l dng gii hn.

Sau khi chia (5.105) cho (5.106) ta c:
iC(O2 )
id

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

Sau khi bin i (5.109) ta c:

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)

v sau khi chia hai v cho id ta c:

O Fc
exp 4 2

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

kh oxi b khng ch bi giai on chuyn in tch, ngha l:

O2 Fc
o
iC(O2 ) = iO
exp
4

2
RT

Ngc li, khi c phn cc ln c >>

RT
ZF

(5.112)

th s hng A rt ln so vi 1, t (5.111) ta

c:
iC(O2 ) = id

(5.113)

Trong trng hp ny ng hc in ho ca s kh oxi b khng ch bi giai on

khuch tn chuyn oxi t th tch vo b mt in cc.
Vy:

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 (2) >

CO2 (1) ;

CO2 (1) .

b) Gin EVAN i vi h kim loi b n mn trong mi trng cht in li cha oxi

vi nng CO2 (1) < CO2 (2) : 1. CO2 (1) ; 2. CO2 (2)

Trong iu kin DO2 v khng i th dng n mn im = iC(O2 ) = id ph thuc vo

nng oxi ho tan trong mi trng n mn.
Trn hnh 5.16 trnh by s ph thuc ca th phn cc E(V) hoc qu th (V) vo lgiC
i vi kim loi b n mn trong mi trng cht in li c mt oxi.

5.7 S th ng ho kim loi

5.7.1 Kim loi hot ng v kim loi th ng
S th ng ho kim loi l mt hin tng quan trng v mt s ln cc kim loi nh Al,
Mg, Ni, Cr, Mo, Ti, Zn, Fe v cc hp kim thp khng g, cc hp kim c bit u c kh
nng th ng trong mi trng n mn.
Nhng kim loi v hp kim b th ng l nh s tn ti mng mng oxit c nanomet
trn b mt kim loi hoc cn gi l lp phim th ng c tc dng ngn cch b mt kim loi
vi mt trng n mn, v th tc n mn kim loi b gim i ng k.
Khi kim loi tip xc vi dung dch cht in li ti khong th dng xy ra phn ng
anot:
M+

z
2

H2O MOz/2 + zH+ + ze

(5.115)

v trn b mt to mng oxit, kim loi i vo trng thi th ng.

Ngc li, cc kim loi hot ng khi ho tan vo dung dch cht in li gn lin vi s
chuyn in tch trn b mt gii hn pha kim loi - cht in li. Cc ion kim loi c to ra
v di chuyn vo dung dch b hirat ho hoc to thnh cc hp cht phc.

93

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

Kim loi

Ho tan hot ng

Ho tan th ng

Fe

Fe2+

Fe3+

Ni

Ni2+

Ni3+

Cr

Cr2+

Cr3+

Thng thng, tc ho tan kim loi trong min th ng rt nh so vi s ho tan

trong vng hot ng.

5.7.2 Cc phng php th ng ho kim loi

C hai phng php a kim loi t trng thi hot ng sang trng thi th ng:
S phn cc anot kim loi trong mi trng cht in li bng dng ngoi.
Nhng kim loi vo dung dch cht in li c sn cc cht oxi ho thch hp (c cp
oxi ho kh c in th kh dng nm trong khong th ng).
5.7.2.1 S th ng ho kim loi bng dng ngoi

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

1. AB - Vng hot ng; 2. CD - Vng th ng; 3. DH - Vng qu th ng;

BC - Vng chuyn tip i vo 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

Trn hnh (5.19) cho thy :

Vng (1) gi l min hot ng, theo ng O1A st b ho tan theo phn ng:
Fe 2e Fe2+

96

ng hc ho tan st c khng ch bi giai on chuyn

in tch. Tc ho
tan st xy ra rt ln vi mt dng khong 2.103 A/m2 v hnh thnh sn phm FeSO4,
lng sn phm ln khng khuch tn kp vo dung dch, khi ng hc c khng ch
bi s khuch tn c th hin trn on AB.
Ti gi tr th dng hn +0,5 V mt cht thi, mt dng gim t ngt khong 105
ln so vi mt dng iCr v trn b mt st to mng th ng theo phn ng:
2Fe + 3H2O Fe2O3 + 6H+ + 6e

(5.117)

Trong min th ng CD gi tr mt dng rt nh v khng ph thuc vo th in

cc, v tc ho tan rt chm ca mng c khng ch bi phn ng:
O2(oxit) + 2H+ H2O

(5.118)

Mng th ng Fe2O3 rt mng, c 50 .

Nu ngt dng in phn cc t dng ngoi gi tr th t vng th ng CD dch chuyn
v pha m mt cch t din bin v mng th ng b ho tan dn do oxit phn ng vi ion
H+. Ti gi tr th m mng th ng bt u b ho tan gi l th Flade. Thng gi tr th
Flade EF gn trng vi th th ng EP v nm trong vng chuyn tip BC.
Nu dch chuyn th v pha dng hn th cn bng oxi - 2 th trn in cc xy ra s
phn hy H2O gii phng oxi:
2H2O O2 + 4H+ + 4e

(5.119)

ng thi c th xy ra phn ng:

Fe Fe3+ + 3e
5.7.2.2

(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

Nhnh phn cc catot XY ca h oxi ho kh ct ng phn cc anot ho tan kim loi

th ng ABCDH ti im O nm trong vng th ng. Ti Em chnh bng ERedox v mt
dng n mn chnh bng dng th ng. Trong iu kin kim loi hon ton b th
ng.
Vy trong mi trng c sn mt h oxi ho khi kim loi nhng vo v s th ng ho
din ra mt cch t din bin nu:
v

Em = ERedox > EP

(5.121)

(i )

(5.122)

ox
c

Cr

> iCr

Nu thiu mt trong hai iu kin (5.121) v (5.122) th kim loi khng th b th ng

c.
Trn hnh (5.20) h oxi ho c th in cc ERedox2 > EP, ng phn cc catot ca h
X1Y1 ct ng phn cc ho tan anot kim loi ABCD ti im I ng vi dng ho tan ln.
Vy kim loi khng tn ti trng thi th ng v cn gi l s th ng khng bn vng.
Tng t trn hnh (5.20) i vi h oxi ho kh c th in cc ERedox3 < EP, ng
phn cc catot ca h X2Y2 ct ng phn cc ho tan anot kim loi ABCD ti P c dng n
mn ln. Vy kim loi khng th tn ti trng thi th ng v khng p ng c cc iu
kin (5.121) v (5.122).
V d 1: Thp trong dung dch pH > 10 c mt oxi v khng c cc anion halogen d
dng b th ng (thp trong b tng).

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

V d 2: St b th ng trong axit HNO3 c vi t trng 1,42 (kg/l).

Phn ng oxi ho kh:

3 + 3H + 2e U HNO2 + H2O
+

Gi tr th tiu chun o / = 0,94 V. Gi tr ny ln hn EP v h ny tha mn cc

3

iu kin (5.121) v (5.122), kim loi rt d dng i vo trng thi th ng v tc kh ca

cht oxi ho 3 rt ln, in th Em gn trng vi th oxi ho kh ERedox.
V d 3: i vi h pin thng kh, bnh thng khi nng oxi cng ln th tc n
mn cng ln, v phn ng kh xy ra cng d dng.

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

Mng th ng trn b mt kim loi c chiu dy c nanomet, v vy vic xc nh thnh

phn v cu trc mng l hon ton khng n gin. a s mng th ng c kh nng dn
in tr trng hp mng th ng trn kim loi nhm v titan tinh khit khng dn in v
khng c vng qu th ng trn ng phn cc anot.
Cn phi lu rng trn b mt kim loi c th ng hon ton song vn c th xy ra
hin tng n mn cc b do s ph hu mng mt cch cc b bng phng php ho hc
hoc c hc. V d trong mi trng c mt cc ion halogen Cl, Br, I.
Ti ch khuyt tt trn mng th ng xy ra phn ng:

100

Me + Cl + H2O MeOHCl + H+ + 2e

(5.123)

v dn n s axit ho cc b ngn cn s ti th ng. Tc n mn ti cc ch khuyt

tt xy ra vi tc ln dn n s n mn im (pitting corrosion).

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

Tt nhin thnh phn hp kim c nh hng n mt dng th ng iP. V d khi tng

hm lng molipen trong thp khng g th kh nng th ng tng ln ngha l dng iP gim
(xem hnh 5.24).

101

Hnh 5.24
ng phn cc anot ca hp kim Fe13CrxMo trong dung dch HCl 1M

0 - Fe13Cr ; 1 - Fe13Cr1Mo ; 2 - Fe13Cr2Mo ; 3 - Fe13Cr3,5Mo ; 4 - Fe13Cr5Mo.

(Chi tit v vn hp kim s c nghin cu trong phn kim loi hc).
Ngoi thnh phn ca hp kim c nh hng r rt n kh nng th ng ca kim loi,
cng cn phi lu pH ca mi trng, cc tp cht c mt trong mi trng c nh hng
ng k n kh nng th ng ca kim loi.
Kim loi i vo trng thi th ng trong mi trng n mn th th ca kim loi oxit tip
xc vi mi trng n mn c tnh theo phn ng:
Me +
hoc

z
2

H2O ez / 2 + zH+ + ze

ez / 2 + zH+ + ze U Me +

z
2

H2O

(5.124)

25oC gi tr th in cc oxit vit cho phn ng (5.124) c dng:

oxit

hoc
Gi tr ooxit

oxit

Me

Me

= ooxit
= ooxit

Me

+ 0,059lg aH+
0,059pH

(5.125)

Me

thay i theo bn cht ca kim loi. V d:

Me

ooxitCr

Cr

< ooxitNi

Ni

< ooxitFe

Fe

102

Kim loi i vo trng thi th ng th th th ng Ep phi dng hn th thun nghch

ca h oxit kim loi v kim loi - ez / 2 /Me (oxit/Me).
Gi tr th tiu chun ca h in cc oxit c trnh by trn bng (5.2).
Th tiu chun oxit c gi tr cng thp, s hnh thnh cng d dng khi dung dch c mt
proton, ngha l cng d dng b th ng v nu bn chng n mn cng cao th mng th
ng c tnh bo v chng n mn cng cao. V d mng oxit trn kim loi Cr, Ti, Ta
Mt khc, theo phng trnh (5.125) th Eoxit/Me gim khi pH tng v khi s ph thuc
ca th oxit vo pH c th ngoi suy c th tiu chun ooxit / Me . C nhng trng hp gi
tr ooxit / Me ngoi suy khng trng vi cc gi tr trong bng (5.2) nu trn. S khc bit ny c
th gii thch bng s khc bit v h s t lng ca kim loi v oxit tnh theo cng thc v
oxit kim loi c hnh thnh trong sut qu trnh to mng th ng.
Bng 5.2. Cc gi tr Go tiu chun to oxit

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

PbO (hirat hex)

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:

1.12.1 n mn tip xc (cn gi l n mn Ganvanic)

Khi c hai kim loi khc nhau tip xc vi nhau hoc hp kim c thnh phn khc nhau
tip xc vi mi trng cht in li sinh ra hin tng n mn tip xc. Qu trnh n mn
din ra nh l s hot ng ca mt pin in khp kn mch. Tc n mn ph thuc vo
hiu s in th n mn (xem bng 6.1) ca hai kim loi trong dung dch cht in li v ngoi
ra n cn ph thuc vo mt s yu t khc nh in tr ca dung dch cht in li, pH, nhit
mi trng
Bng 6.1 Gi tr th n mn Em ca mt s kim loi trong nc bin nhn to 25oC

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

1- ng phn cc catt thot H2 trn km; 1- ng phn cc ho tan km;

2- ng phn cc catt thot H2 trn st; 2- ng phn cc ho tan st;
3- ng phn cc thot H2 trn st v km
Khi Zn tip xc vi thp (Fe) trong mi trng axit H2SO4 long khng c oxi s tn ti
cc pin in sau y:
+ Nu Zn v Fe khng tip xc ta c hai pin tch ri nhau:
() Zn/H2SO4/(H2) Zn (+)

(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.

+ 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
v tng dng n mn ca hai kim loi km v st hoc bng tng
ng vi dng n mn im
Zn
2
dng n mn iH
trn hai kim loi (xem hnh 6.2). Gi tr ny ln hn dng n mn im
hoc
c
Fe
im .
H2
H2
Zn + Fe
Zn
im
= im
+ 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
nm gia 2 gi tr th n mn ring bit ca st v niken, ngha l:
m
Ni + Fe
EFe
< ENi
m < Em
m

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

1- ng phn cc thot H2 trn st v niken; 2a- ng phn cc ant ho tan niken.

2b- ng phn cc ho tan st; 3- ng phn cc ant ho tan ng thi niken v st;
3a- ng phn cc catt thot H2 ng thi trn niken v st
V d 3: H tip xc gm mt kim loi b n mn c ghp vi mt in cc khng b
n mn (vt liu tr - v d Pt, cacbon, v.v).

Xt h km tip xc vi Pt (Zn-Pt) c t trong mi trng H2SO4 long.

Pin n mn tng t pin in: () Zn / H2SO4 / Pt / Zn (+)

(6.4)

Zn 2e Zn2+

Ti anot km b ho tan:

ng thi ti vng catot ion H+ c kh thnh kh H2:

2H+ + 2e H2
trn c hai phn kim loi Pt v Zn. V th tc gii phng H2 tng ln dn n tng s
ho tan km. iu ny c th hin trn hnh (6.4).
Trong mi trng axit, tc gii phng H2 trn nn Pt cao hn trn nn Zn, v vy khi
Zn tip xc vi Pt tc thot hiro tng ln ng k v th tng dng n mn cng nh th
Zn + Pt
n mn Em
ti ch tip xc dch chuyn dn v pha gn vi th cn bng thot hiro.
Vy:

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

1- ng phn cc ant ho tan km; 2- ng phn cc catt thot H2 trn km;

2a- ng phn cc catt thot H2 trn Pt; 2b- ng phn cc thot H2 trn h Zn+Pt

108

C rt nhiu yu t nh hng n qu trnh n mn Ganvanic, song c hai yu t quan

trng:
dn in ca dung dch cht in li: Nu in tr dung dch ln, v d nc sng, ao
h dn n s gim tc n mn ni chung, song c th dn n tng tc n mn cc b
ti vng tip xc.
Khi hai kim loi tip xc vi nhau trong mi trng n mn, nu din tch ca kim loi
c in th dng hn cng ln (vng catot), phn cc catot cng gim th tc n mn
cng ln. V vy, chng n mn kim loi in ha, nu din tch ca vng anot so vi vng
catot cng b th dng n mn cng gim (xem hnh 6.5).
Ngoi ra cn mt s yu t khc v d nhit , pH dung dch cng nh dng trao i io
i vi qu trnh gii phng H2 trn cc nn kim loi khc nhau u c nh hng n tc
n mn tip xc.
lm gim tc n mn tip xc ca mt thit b hoc ca mt cu kin no trong
mi trng n mn cn phi trnh s tip xc ca hai kim loi c th in cc khc nhau;
chn t l din tch vng catot v anot thch hp. C th bo v chng n mn bng phng
php bo v catot bng cch gn mt kim loi hot ng hn vo ch tip xc, v d km
hoc nhm hoc Mg, kim loi ny c in th m hn cc kim loi tip xc.

Hnh 6.5a
ng phn cc ca h n mn tip xc Zn-Pt trong mi trng axit (din tch Pt tng ln)

1. ng phn cc catot kh H+ trn nn Zn;

2. ng phn cc catot kh H+ trn nn Pt c din tch nh hn;
3. ng phn cc catot kh H+ trn nn Pt c din tch ln hn;
4. ng phn cc catot tng cng kh H+ trn nn Pt-Zn vi din tch ln

109

1.12.2 S n mn kim loi do s chnh lch kh

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.
2
5

3
1

1. in cc st;

2.Tip xc ng, ngt mch;

3. Cu ni hai dung dch

(NaCl);

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

ng CC2 - Phn cc catot vi p sut O2 ln ( PO22 )

ng CC1 - Phn cc catot vi p sut O2 nh ( PO1 2 )
ng CC1 - Phn cc catot vi p sut O2 rt nh
ng AA1 - Phn cc anot ho tan st
Ta xt trng hp sau:
i vi cc bn tri c p sut oxi ln PO22 (hnh 6.5b) st b n mn gn lin vi s tiu
th oxi vng catot theo phn ng:
O2 + 4e + 2H2O 4OH

(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.

Cc bn phi ca hnh (6.5b), p sut kh O2 rt nh ( PO1 2 ) st b n mn km theo s tiu

th O2 theo phn ng (6.6) vi dng n mn iFe
m1 = i d1 (dng gii hn ca qu trnh tiu th
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.
Fe
PO22 > PO1 2 ng vi iFe
m2 > i m1

111

Nu nng O2 rt nh, dng khuch tn oxi rt nh id1 , phn ng (6.6) xy ra vi tc

rt nh, song nu phn cc m tip tc theo ng CKC3 s xy ra phn ng catot:
2H2O + 2e H2 + 2OH

(6.7)

on thng KC3 ct ng 1, im ct tng ng vi dng n mn iFe

m1' > i d1' .
Nu ng kho tip xc 2 ni in cc 2 v 1, din tch anot b n mn gp 2 ln, dng
anot tng gp 2 ln, dng catot b khng ch ch yu bi dng gii hn id2 . Khi th n
Fe
Fe
mn ca hai in cc 1 v 2 ghp li Eghp
m nm gia hai gi tr Em1 v Em2 ng vi im
ct ca hai ng tng cng anot P1P, catot QQ1.

Dng n mn ca h ghp ighp

m > i d2 > i d1
Fe
Fe
ighp
m > i m2 > i m1

hoc

Tm li, i vi pin thng kh, dng n mn tng v cn lu rng c trng hp xy ra

ngc li nu khu vc c p sut PO2 ln, phn ng kh (6.6) xy ra lm cho pH dung dch
tng ln dn n s th ng, cn li khu vc c PO2 thp s ho tan st li lm gim pH theo
phn ng:
Fe

+ H2O

FeOH+ + H2O
Fe

FeOH+ + H+ + 2e

v km theo phn ng ho hc

Fe(OH)2 + 2H+

+ 2H2O Fe(OH)2 + 2H+

(6.8)

S to thnh ion H+ lm gim pH mi trng v thc y s ho tan st. Trong trng

hp ny ti khu vc c nng PO2 thp li c tc n mn ln hn.
Hin tng n mn chnh lch kh thng xy ra trong cc trng hp sau:
1. n mn khe

Ti nhng khe gia cc mt bch c lp m ca cc ch ni hai ng kim loi, hoc di

cc vt m tn c (tn riv) hoc c c xit c th sinh ra n mn cc b v trong cc khe
nng oxi ca khng kh ngho hn pha ngoi.
2. n mn ti vng mn nc

Ti nhng vng mn nc, v d vng mn nc ca chn cu st cm xung sng vng

nc l, mn nc ca thnh tu bin v.v ti c 3 pha tip xc vi nhau: khng kh
(cha oxi), pha rn (thp), pha nc (dung dch mui hoc nc l) v c th tn ti mt pin
hot ng th ng do s chnh lch v thong kh (xem hnh 6.7).

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

Vng mn nc ti lp g 2 c cu trc xp. S hnh thnh lp g din ra theo cc phn

ng:
Ti vng anot ngho oxi st b ho tan:
Fe 2e Fe2+
Ti vng mn nc giu oxi hn v ng vai tr catot xy ra phn ng:
1
2

O2 + 2e + H2O 2OH

v hnh thnh lp kt ta:

Fe +

1
2

O2 + H2O Fe(OH)2

ng thi xy ra phn ng ho hc:

2Fe(OH)2 +
v

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

Lp g xp b kim ho v di lp g ny thp b th ng.

Vng 1: ngho oxi nhng li b n mn mnh hn (ho tan hot ng) l do s hot
ng ca pin hot ng - th ng.
3. n mn do lng ng

Dng n mn ny tng t n mn khe di cc lp ct, bn, sn phm n mn lng

ng. Ti nhng ch b che khut ngho oxi v b n mn (xem hnh 6.8).

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

1.13 n mn l hay cn gi l n mn im (pitting corrosion)

n mn l l mt dng n mn cc b to ra cc l c kch thc nh, su ca l c
th ln hn ng knh ca n. Dng n mn ny xy ra trn cc kim loi, hp kim c mng
th ng (Al, Ni, Ti, Zn, thp khng g) hoc c cc lp ph bo v b xuyn thng.
Hin tng n mn ny thng xy ra khi mi trng n mn c cha cc cht oxi ho
(NO3, NO2, CrO42) ng thi c mt cc cht hot ho Cl, Br, I (v d mi trng nc bin)
ca cc thit b my mc
Hnh dng cc l do n mn gy ra ph thuc vo bn cht cc lp ph. Trc ht ta xt
c ch n mn l i vi kim loi c lp ph l mng th ng.
1. Lp ph l mng th ng

Mt s kim loi hay hp kim c bn chng n mn cao l nh c lp th ng bm trn

b mt kim loi ngn cch kim loi vi mi trng n mn. V d: Fe, Al, Ni, Cr, Ti v cc
hp kim Fe-Cr, FeCr-Ni song trong mi trng xm thc c cha cc ion halogen Cl, Br,
I th chng s b n mn l bao gm cc giai on sau:
S hnh thnh l

Cho n nay vn cha c c quan nim r rng v s hnh thnh l. Song c th gi

thit rng: ti mt s ch b mt mng th ng cha hon chnh c s hp th cc ion
halogen, v d Cl, ti kim loi b ho tan vi tc ln to l pht sinh n mn im v
to nn cc mui d tan. Nhng v tr c mng th ng cha hon chnh thng l bin gii
gia kim loi v tp cht phi kim. Ti mng th ng khng bo v c kim loi v d
hp th cc ion halogen. Gi tr th , ti lp th ng bt u b xuyn thng, n mn im
bt u gi l th n mn l (th pitting - El) (xem hnh 6.9).
Trn hnh 6.9 ng cong OABCD l ng phn cc ho tan kim loi trong dung dch
khng cha ion halogen.
OA- Vng ha tan hot ng ca kim loi Me ze Mez+
AB- Kim loi i vo trng thi th ng:
Me + zH2O Me2Oz + 2ze + 2zH+

(6.9)

114

BC- Vng th ng - c mng th ng

CD- Qu th ng, trong dung dch nc xy ra phn ng gii phng oxi:
2H2O O2 + 4e + 4H+

(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

Ti im C ng vi in th bt u n mn l El, mng th ng bt u b chc thng,

n mn l bt u (Z+= 3):
Me + H2O + X MeOHX+ + H+ + 3e

(6.11)

Cc gi tr th trong min th ng m hn th bo v Ebv th ti khng xy ra s n

mn l. Gi tr th n mn l El cng dch chuyn v pha m th kh nng n mn l xy ra
cng d dng. V d trong mi trng NaCl 0,1N, gi tr El ca Al bng ElAl = 0,43 V v
ElNi = 0,28 V th Al b n mn l d dng hn Ni. Mt khc, khi tng nng ion Cl th gi
tr th El s dch chuyn v pha m nhiu hn, ngha l s n mn l xy ra cng d dng.
i vi mng th ng ca Fe tn ti dng FeOOH v b ho tan rt chm:
FeOOH + H2O Fe3+ + 3OH
Khi c mt ion Cl mng oxit st d dng b ha tan:
FeOOH + Cl FeOCl + OH
FeOCl + H2O Fe3+ + Cl + 2OH
FeOOH + H2O Fe3+ + Cl + 2OH
y c th xem ion Cl ng vai tr l cht xc tc cho qu trnh ho tan mng th
ng.
S pht trin l

Ti v tr n mn l, s n mn kim loi lm cho pH ca mi trng gim (theo phn ng

6.11) v vi s c mt ion halogen trong l hn ch hin tng ti th ng.

115

Mt khc v cc l nh, s l t cho nn din tch ho tan anot ca kim loi rt b so

vi din tch mng th ng ng vai tr l catot cho nn mt dng ho tan ti cc l rt
ln, khi xem s ho tan ca cc l nh l cc anot hi sinh. V vy m kch thc cc l to
dn ln, ngha l c s pht trin l. i vi nhng kim loi c mng th ng dn in rt
km, v d trn kim loi Al, Ti th s pht trin l din ra rt chm.
Ngoi cc anion halogen, mt s cu t c mt trong kim loi, v d cc sunfua trong
thp khng g, hoc cc kim loi dng hn c mt trn b mt th ng (v d ng trn b
mt Al) c tc dng kch thch s n mn l.
Hnh 6.10 m t dng n mn l ca thp th ng trong dung dch trung tnh c mt Cl.

Hnh 6.10
Dng n mn l ca thp th ng trong mi trng c mt Cl

C tc gi cho rng s pht trin n mn l tng t n mn khe. Di y gii thiu

mt s bin php bo v kim loi th ng khi s n mn l.
La chn kim loi
Thp khng g hp kim Fe-Ni-Cr c th xy ra n mn l trong nc bin. Hp kim Fe,
Ni, Cr, Mo c kh nng chng n mn cao trong mi trng c ion Cl, hp kim cha Ti cng
c kh nng chng n mn l do ion Cl gy ra...
Thay i mi trng: loi ion Cl, thm vo mi trng cc cht hn ch s hp ph
ca ion Cl, v d OH hoc ion Cr2O7 hoc cc cht c ch khc c th l NaNO2, NO3...
Dch chuyn th vo vng th ng.

1.14 Mt s dng n mn khc

6.5.1 n mn ranh gii
Hin tng n mn ranh gii c lin quan n s tn ti ca cc pha d th ti bin gii
cc ht trong hp kim a tinh th, v d thp FeNi8Cr18, khi lm ngui dn t 1100oC c dng
tinh th cacbua crom (CrFe)23C6 s kt ta bin gii ht. Lng crom bin gii ht gim
v mt kh nng th ng, vng th th ng b hp li, dng th ng ln ln v s ho tan
trong min th ng ln ln. Vy mt in th th ng nht nh bn trong mt bin gii b
th ng, cn bin gii ht th hot ng, trong trng hp ny c hin tng n mn gia
cc tinh th.
trnh hin tng n mn gia cc tinh th i vi thp hp kim FeCr, trong qu trnh
thp cn trnh hin tng kt ta hoc dng thp c cha mt s nguyn t nh Ti hoc Nb,
chng kt hp vi cacbon.

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

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

+ Tc th ng, nu tc ti th ng din ra qu chm th tc ho tan kim loi

s xy ra ng k ti cc u mt v vt nt bn cnh. Nu s ti th ng din ra nhanh th
tc lan truyn vt nt s b chm li.
i vi kim loi th ng, khi dch chuyn th v pha qu m s c hin tng n mn
nt do hiro thm trong kim loi, iu ny cng cnh bo v tc hi ca s bo v catot qu
mc. Ngc li, khi phn cc anot vi th dng kh cao vt ngng s to ra oxi cng dn
n s n mn nt.
Nu trn b mt kim loi c s hp ph c bit ca cc phn t hot ng t dung dch
cng lm suy gim bn c hc ti u mt cc vt nt dn n ph hu lin kt gia kim
loi-kim loi lm cho kim loi d dng b ph hu. V d s hp ph ca cc nguyn t hiro
s lm yu lin kt kim loi- kim loi
c) Cc bin php chng n mn do ng lc

C mt s bin php sau:

Thay i iu kin ng lc. V d thay i thit k sao cho cng ng lc gim ti
a hoc x l nhit lm gim ni ng lc.
Thay i mi trng n mn. V d loi cc cht gy n mn nt (ion Cl) hoc thm
vo mi trng cht gy th ng hoc c ch qu trnh n mn.
Thay i th in cc a kim loi vo trng thi bn vng.
Thay i cu trc kim loi: lm gim khuyt tt, gim s kt ta ti bin gii ht bng
cch nhit.
Sn ph b mt kim loi, ngn cch b mt kim loi vi mi trng n mn.

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.

1.15 nh hng ca mi trng n qu trnh n mn kim loi

6.5.1 n mn trong mi trng kh quyn
Hin tng n mn kim loi trong iu kin kh quyn m l n mn in ho. Do s
ngng t hoc ngng ng ca nc trn b mt kim loi c mt mng mng nc, s ho
tan ca cc kh CO2 hoc SO2 to ra dung dch c pH thp v kim loi b n mn mt cch d
dng. Hn na, s ho tan ca oxi trong khng kh vo mng mng cht in li cng l mt
yu t quan trng i vi qu trnh n mn in ho ho tan kim loi.
n mn kh quyn ph thuc vo nhiu yu t sau y:
a) m

m l iu kin cn phi c xy ra hin tng n mn in ho, nhng cha phi l

iu kin . c th xy ra hin tng n mn in ho trn b mt phi tn ti mt lp

119

mng mng cht in li gm mng mng nc v cc cht in li ho tan, v d Cl, CO32,

SO32 Tu theo m trn b mt m ngi ta phn loi n mn kh quyn:
n mn kh quyn kh - kim loi tc dng trc tip vi oxi to ra mng oxit cc mng,
c th xem l cc phn ng ho hc, v khng gy ra hin tng n mn kim loi ng k,
nhng khi c tp cht n mn th tc n mn c th tng ln.
n mn kh quyn m - trong iu kin m vi m tng i H < 100%, thng ln
hn 70%, trn b mt kim loi c lp mng mng nc v c tp cht th xy ra n mn theo
c ch in ho. V d Cu, Ni, Zn b n mn trong kh quyn khi m tng i ln hn
60%.
ng nhin tc n mn ph thuc vo m tng i ca khng kh, m ca kh
quyn v tnh ht m ca sn phm n mn.
Cn nhc li rng m tng i H c tnh bng cng thc sau:
H=

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

Cc mng m nc to ra trn b mt kim loi, v d khi m cao, sng m thng

cha tp cht: kh oxi hoc kh CO2 ho tan ( min nng thn, min ni), cc kh CO2, SO2,
cc oxit nit (NxOy), kh H2S (vng cng nghip), ion Cl (vng bin, ven bin). Cc tp cht
ny gp phn lm tng tc ph hu kim loi (xem hnh 6.11).

Hnh 6.11
Tn tht trng lng (g/m2) ca thp cacbon theo thi gian (ngy)

120

1 - n mn kh quyn c kh SO2; 2 - n mn kh quyn khng c kh SO2

i vi khng kh sch, s n mn xy ra vi tc rt nh (ng 2 hnh 6.11). Sau khi

c mt kh SO2 trong khng kh m tc n mn tng ng k. Ngoi kh SO2, cc kh CO2,
NO2, Cl u l tc nhn gy ra n mn kh quyn.
c) C ch n mn in ho trong mi trng kh quyn

n mn trong mi trng kh quyn l n mn in ho vi qu trnh catot, trong nhiu

trng hp l s kh oxi.
Anot:
Catot:

Me ze Mez+
z
2

O2 + ze + zH2O 2zOH

ng hc ca qu trnh ho tan kim loi ph thuc vo chiu dy lp mng m trn b

mt kim loi.
Vi mi trng khng kh kh, m thp, dy mng m khong 10 nm th c ch n
mn xy ra ch yu theo c ch ho hc.
Vi dy lp mng m c 10 nm 1 m, trn b mt c lp cht in li, s n mn
kim loi b khng ch bi qu trnh anot, v mng mng s khuch tn din ra nhanh, ngha
l qu trnh catot din ra nhanh. Nu c sn phm n mn dng oxit bao ph ln b mt th
qu trnh anot din ra phc tp hn.
Nu b mt lp mng mng m c dy t 1 m n 1 mm, oxi ca khng kh xm
nhp vo b mt kim loi kh khn. V th qu trnh n mn kim loi b khng ch bi phn
ng catot.
Khi lp mng m c dy ln hn 1 mm th s n mn kim loi xy ra tng t trng
hp kim loi ho tan trong dung dch cht in li (Ct st li n tn ti 2500 nm,
thnh phn tp cht ca ct thp: Si 0,05%, S 0,006%, P 0,114%, C 0,08%, Mn vt.
Ct thp ny c bn chng n mn rt cao v thp sch v trn b mt kim loi lun lun
kh ro).

6.5.2 n mn kh quyn vng thnh ph v khu cng nghip

thnh ph v khu cng nghip c mt s kh thi v ch yu l SO2 t cc l t than,
t du. Khi kh thi ny ho tan vo nc s axit ho mi trng nc v lm tng tc n
mn kim loi. Tc n mn kh quyn c tnh theo cng thc:
P = at b (g / m2 )

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

i vi n mn kh quyn, ngoi cc tp cht gy n mn th thi gian lu m (TOW) tc

l khong thi gian khng kh c m tng i H > 80% v nhit ln hn 0oC ng mt
vai tr rt quan trng quyt nh tc n mn kim loi.
Nhng mng mng do nc ma hoc do sng trn b mt kim loi thng c m
gn bng 100%.
vng nng thn kh quyn t tp cht c hi cho nn tc n mn kim loi nh.
Vic nghin cu cc bin php chng n mn kh quyn rt c ngha thc t. C th nu
ln mt s bin php chnh sau:
To ra cc lp bao ph, sn hu c, c lp ph v c, hoc xi m ngn cch kim loi vi
mi trng gy ra n mn. V d sn ph bo v cu st, tu thuyn, cc cu kin khc: t,
tu ho, m cc ph tng t, xe my
Chn cc kim loi c bn chng n mn cao: thp khng g, cc loi hp kim.
i vi cc cu kin nh v lu gi trong kho c mt cc loi cht c ch bay hi bo
qun trong khng kh kh.

6.5.4 n mn trong mi trng t

Trong lng t, c bit cc khu cng nghip c rt nhiu thit b chn ngm di t:
h thng ng dn nc, dn kh ga, cp in, ng ng dn nhin liu lng, xng du c
th b n mn lm gim tui th ca chng v i khi cn lm gim cht lng sn phm
nc ( nhim nc, gim cht lng xng du).
Tc ph hu cc cu kin do n mn ph thuc vo a hnh. nhng v tr cao, kh
ro, khng c cc m mui th tc n mn kim loi rt thp.
Hin tng n mn kim loi c tc ng k thng xy ra nhng vng m, c tp cht
gm cc mui v c, v d vng t m ven bin.
nh gi kh nng n mn kim loi ca mi trng t ngi ta dng ch s pH hoc
dn in ca t.
Vi pH = 5 8 v nn t m, mi trng axit c dn in tt, kim loi d dng b n
mn. Trong cng mt iu kin, t ct gy ra n mn cao hn t st v d dng thng kh
oxi. Cn lu rng trong mi trng t, s c mt ca vi sinh vt cng nh hng ng k
n tc n mn.
S n mn kim loi trong mi trng t l n mn in ho vi catot kh oxi, i khi
kh ion H+ nu mi trng n mn l axit.
Do cu trc ca t khng ng nht cho nn s thng kh khng u v thng gy ra n
mn thng kh, khi ni c nhiu oxi ng vai tr l catot cn vng t oxi ng vai tr l
anot, phn ng xy ra ph hu kim loi.
Dng n mn kim loi trong t rt a dng, thng l n mn cc b nn kim loi b ph
hu dng n mn im, h su, dng r
hn ch kh nng n mn do mi trng t, cc cu kin phi c bo v (sn ph
bc kim loi bng vt liu polyme, sn bitum) hoc cc loi sn v c (sn xi mng)
Thng thng, ngi ta s dng phng php in ho bo v catot bo v cc ng ng
dn nhin liu nm trong lng t.

6.5.5 n mn trong btng ct thp

122

Ngy nay, vic nghin cu s n mn v bo v cc cng trnh btng ct thp l mt

ti kh hp dn, c nhiu nh khoa hc nc ngoi v trong nc quan tm v s lng
cng trnh btng ct thp rt nhiu: cc cng trnh dn dng nh ven bin, cu cng ven
bin, cu cng bin, cc cng trnh khai thc du kh v.v
Btng ct thp gm hai phn: phn v l vt liu nhn to gm cc thnh phn c t
l hp l: cht kt dnh xi mng, nc, ct liu th (si ct) v cc ph gia khc, chng c
trn vo nhau sau c thnh khun v phn th hai l ct li bng thp.
Trong qu trnh ng rn ca btng, cc thnh phn ca khong xi mng b thu ho v
to mi trng kim (pH = 13 14). Trong mi trng ny ct thp b th ng.
Phn ng thu ho (hirat ho) ca cc khong silicat nh sau:
2(3CaO.SiO2) + 6H2O 3CaO.2SiO2.3H2O + 3Ca(OH)2
2(2CaO.SiO2) + 4H2O 3CaO.2SiO2.3H2O + Ca(OH)2
i vi khong C3A phn ng xy ra:
3CaO.Al2O3 + 6H2O 3CaO.Al2O3.6H2O
2(3CaO.Al2O3) + 21H2O 4CaO.Al2O3.13H2O + 2CaO.Al2O3.8H2O
Khi c mt thch cao xy ra phn ng to thnh ettringit:
3CaO.Al2O3 + 3(CaSO4.2H2O) + 6H2O 3CaO.Al2O3.3CaSO4.12H2O
Ettringit l cc tinh th hnh kim c hnh thnh nhanh trn khong C3A cha thu ho
to lp v bc khng cho nc thm qua. V vy thch cao c dng lm ph gia iu chnh
thi gian ng kt xi mng.
Qu trnh thu ho din ra sut thi gian s dng btng.
Nu lp v cht xt c kt cu tt th ct thp lun lun trng thi th ng v khng
b n mn.
Nu lp v btng qu mng hoc c kt cu xp th oxi s xm nhp vo ct thp v
gy ra n mn. ng nhin khi btng ct thp ngm trong nc, lng oxi thp, kh xm
nhp ct thp v s ph hu ct thp cng b hn ch.
Trong nc bin cha nhiu ion Cl, s xm nhp ca n vo cu trc b tng s nh
hng ln n tui th ca cc cng trnh.
Ion Cl xm nhp vo b tng theo c ch khuch tn v thng tn ti cc dng: hp
ph vt l trn b mt rn ca l xp, tham gia lin kt ho hc to C3A.CaCl2.10H2O hoc
C3A.3CaCl2.3H2O
Nu tn ti t do trong cc mao qun, l trng ion Cl s ph hu v n mn btng ct
thp.
Qu trnh n mn ct thp btng l n mn in ho. Khi c ion Cl xm nhp vo lp
th ng ca btng, lp th ng b ph v v thp b n mn, pH gim:
Fe 2e Fe2+
Fe2+ + 2H2O + Cl Fe(OH)2 + 2HCl

123

Ngng ti hn ph hu mng th ng v gy n mn ct thp l [Cl]/[OH] = 0,6. Khi

lp th ng b ph v mt phn hoc hon ton th th in cc ca ct thp dch chuyn v
pha m hn, ti ng vai tr l anot v thp b ho tan (xem hnh 6.13).

Hnh 6.12
S n mn ct thp btng

Ti anot:
Tai catot:

Fe 2e Fe2+
1
2

O2 + 2e + H2O 2OH

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

Vi sinh vt thng tn ti trong lng t, y cc b nc ngm, cc b cha nc, y

cc bn cha xng du... S hot ng ca cc vi sinh nh hng n qu trnh n mn kim
loi theo c ch in ho.
S hot ng ca vi sinh hoc sn phm hot ng ca n c tc ng n cc qu trnh
catot hoc anot ca s n mn in ho. C hai loi vi khun nh hng n tc n mn:
vi khun hiu kh v vi khun k kh.
n mn kim loi c vi khun hiu kh:
Loi vi khun hiu kh tiu th oxi, s hot ng ca vi khun ny sinh ra cht thi dng
bn v bm trn b mt kim loi to ra pin thng kh gy ra s n mn in ho ph hu kim
loi. Mt khc, loi vi khun hiu kh oxi ho sulfua, v d vi khun Thiobaccillus, c kh
nng oxi ho nguyn t lu hunh hoc cc hp cht c lu hunh trong kim loi thnh axit
sulfuric H2SO4 theo phn ng sau:
2S + 3O2 + 2H2O 2H2SO4
v to ra mi trng axit lm tng tc ho tan kim loi.
Vi khun oxi ho sulfua hot ng tt trong mi trng axit vi pH = 0 6.
C loi vi khun thc y qu trnh oxi ho ion Fe2+ thnh Fe3+, khi nng Fe2+ gim
v thc y qu trnh anot ho tan st:
Fe 2e Fe2+
Vi khun oxi ho st pht trin tt vng pH = 4 10, sn phm n mn c mu .
Ti nhng ni mng sn b h hng, st b n mn v c Fe(OH)3 kt ta to ra cc g
cng l ni ch n ca cc vi khun k kh.
n mn kim loi c vi khun k kh.
Vi khun k kh ch yu l vi khun kh sulfat (D.desulfuricals). Do hot ng ca chng
cc ion sulfat b kh thnh sulfua theo phn ng:
SO24
S
Vi khun

+ 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
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.

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.

7.1.1 Kim loi en

Thp cacbon thp

Thp cacbon thp l hp kim ca st cha mt lng cacbon t 0,05 1%.

Thp cacbon thp c dng rt rng ri trong ngnh xy dng v gi thnh thp, d to
hnh.
Kim loi ny khng bn, chng n mn km trong mi trng khng kh, trong t cng
nh trong nc t nhin v n thng phi c bo v.
Trong khng kh kh thp ny khng b n mn v c lp mng mng cht st oxit bo v,
nhng nhit cao b n mn.
Trong khng kh m nhit thng, trn b mt thp c mng nc xy ra, phn ng
n mn theo c ch in ho:
Phn ng anot:
Fe + HOH FeOH+ + H+ + 2e
FeOH+ + HOH FeOOH + 2H+ + e
Phn ng ny khng ch s n mn thp trong kh quyn.
Phn ng catot:
3FeOOH + e Fe3O4 + H2O + OH
Tip theo sn phm Fe3O4 tc dng vi oxi v nc:
Fe3O4 +

1
4

O2 +

3
2

H2O 3FeOOH

126

C kin cho rng, trong khng kh sn phm n mn thp l FeOH+ v OH s tc dng

vi oxi v nc to thnh hyroxit, oxit st (II) v oxit st (III) v chng to thnh lp g
st.
Theo thi gian g st pht trin thnh cc lp xp v lm gim tc n mn thp. Nu
trong khng kh c tp cht, v d Cl vng ven bin, s hp th Cl ca cc lp g lm thay
i hnh thi lp g, i khi lm tng tc n mn thp.
S c mt ca SO2 trong kh quyn c th b hp th bi cc lp g v dn n s axit ho
cc lp g, lm tng s kh oxi v tng dn in ca dung dch thc y qu trnh n mn
thp.
SO2 + O2 + 2e SO24
Trong mi trng nc gn trung tnh (nc my, nc bin, nc ao h) tc n mn
kim loi ch yu ph thuc vo tc phn ng catot kh oxi.
2H2O + O2 + 4e 4OH
hoc

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)

trong : P - tn tht chiu dy mm/nm;

CO2 - nng oxi ho tan tnh theo mg/l nc;

- chiu dy lp khuch tn (mm);

K - chp nhn bng 14,3.

Cng thc trn ch p dng cho n mn u, nu c s n mn cc b th vic s dng n
b hn ch.
Trong mi trng axit, tc n mn thp ph thuc vo tc phn ng catot v thp
b n mn ng k nu khng c bo v.
2H+ + 2e H2
hoc khi c mt oxi:
2H+ +

1
2

O2 + 2e H2O

i vi mi trng axit yu, lng ion H+ thp, tc n mn c quyt nh bi giai

on khuch tn ion H+ n b mt kim loi. S c mt ca CO2 vi hm lng cao c tc
dng thc y phn ng catot:
2CO2 + 2H2O + 2e H2 + 2HCO3
v th m tc n mn s tng ln.

127

Trong mi trng t nng oxi thp v vy s n mn thp c gy ra l do hot

ng ca vi khun kh ion sulfat to ra H2S v xy ra phn ng:
Fe + H2S FeS + H2
Thp hp kim thp

Thp hp kim thp gm st v mt lng nh khong di 2% cc nguyn t hp kim

Cu, Ni, Cr, P hoc t hp chng li s to ra vt liu c bn chng n mn cao i vi mi
trng n mn kh quyn.
Trn b mt ca thp hp kim thp to ra lp oxit Fe3O4 c cu trc cht st ngn cn s
tc ng ca mi trng lm gim qu trnh g ho tip theo. Lp bo v ny bn trong mi
trng kh quyn nng thn cng nh khu cng nghip hoc khi thay i thi tit nng ma.
Thp ny c gi l thp thi tit v c dng rng ri trong cng nghip xy dng.
Khi c mt ion Cl trong cc vng kh hu bin v ven bin hoc khi nhng vo nc, lp
oxit ny khng bn vng. Trong iu kin kh hu bin thng s dng thp hp kim ho c
cha cc nguyn t Al, Cr hoc Mo.
Thp hp kim thp nhy cm vi hin tng n mn nt khi tip xc vi cc mi trng
cha cc ion NO3 , OH v NH3 lng.

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.

7.1.3 Thp khng g

Thp cha mt hm lng ln cc nguyn t Cr, Ni, Si (thp hp kim cao) c bn
chng n mn cao v cc ph gia trn d dng to ra cc mng th ng. Hp kim c thnh
phn Cr > 12% d dng b th ng trong dung dch nc do s kh oxi.
Di y l mt s loi thp khng g thng dng c k hiu theo quy c thng dng
(xem bng 7.1).
Loi thp khng g ferit

Loi thp ny hm lng cacbon thp, c 16 30% Cr, i khi c Mo v cc nguyn t

khc. Crom l nguyn t n nh trng thi ferit v gi c cu trc mng lp phng tm.
Thp khng g ferit l loi st t. S kt ta ca cacbua crom lm gim bn chng n
mn nhit cao, n c khuynh hng pht trin ht gy kh khn cho vic hn.

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 khng g Mactensit

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

Thp ny rt bn trong mi trng axit boric, axit limonic

Thp ny b n mn trong dung dch HCl, H2SO4 long, trong H2S v trong cc axit
H2C2O4, HCOOH si v khuynh hng n mn tinh gii, n mn im, n mn khe.
trnh n mn tinh gii ngi ta s dng cc bin php sau:
+ Thm vo hp kim mt s nguyn t nh Ti to ra cc hp cht
cacbua.
+ Gim hm lng cacbon xung di 0,015%, ti nhit 1050
1100oC Cr v C tn ti dng dung dch rn.
+ Nung ln 870oC s ph mng cacbua v san bng hm lng Cr.
trnh n mn thp khng g Ostenit Cr-Ni c th dng phng php bo v catot bng
dng ngoi.
Loi hp kim ny c s dng rng ri trong cng nghip ha cht, dc phm, thc
phm, ch to cc dng c nh bp.

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+

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
hoc

CuCl2 + 1e U Cu + 2Cl

v th in cc:

vi

Cu

aCl = 1 v aCuCl = cCuCl = 10 M

2

th

= 1,94 + 0,059 lg

cb
ECuCl

= 0,160 V

cb
ECuCl

Cu

aCuCl
2

2
aCl

130

Vy ti mt gi tr pH xc nh, ng s b n mn trong dung dch HCl gii phng kh

H2.
Trong nc thin nhin, nc bin l trung tnh hoc hi kim tc n mn ng xy ra
rt chm, mt lng nh ion ng git cht cc vi sinh, hu h, to bm trn nn kim loi
ng.
S km hm qu trnh n mn ng trong cc mi trng trn l v kim loi ng b che
ph bi oxit.
2Cu + H2O Cu2O + 2H+ + 2e
Tc n mn ng khong 25 50 m/nm (im = 2 4.102 A/m2) trong mi trng
2
idO = 0,2 0,3 A/m ). Khi c dng
nc bin tnh (thp hn dng gii hn kh oxi
2

chy v mng Cu2O b ph v ti cc mp nn tc n mn tng ln.

ng bn trong khng kh v c tp cht to vi ng mt s hp cht c tnh bo v
chng n mn, v d CuS, Cu(OH)2CO3, c mt SO2 to ra CuSO4.3Cu(OH)2. Cc mi nh
bng ng c bn chng n mn cao, tui th hng th k.
Cc hp kim ca ng

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.

7.1.5 Titan v hp kim titan

Trong iu kin m, trn mt titan kim loi to ra lp oxit TiO2, n l mng bo v rt tt.
mi gi tr pH mng TiO2 c hnh thnh trn b mt kim loi Ti v rt bn trong a s
cc dung dch kim v axit.
Titan bn trong nc bin, trong dung dch clorua, ClO, HNO3

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.

7.1.6 Niken v hp kim niken

Trong mi trng axit khng c tnh oxi ho: dung dch HCl long, dung dch H2SO4
long niken b ho tan chm hn st. Mng th ng ca Ni km bn so vi mng oxit
crom.
Trong nc bin tnh niken d b n mn im. Niken rt bn trong mi trng kim c,
trong NaOH nng chy. C th dng cc thng bng Ni hoc thng st ph niken cha
kim c.
Hp kim Ni-Cu (70%Ni - hp kim Monel) bn trong nc bin chuyn ng, dng lm
b cha axit HF. Hp kim ny khng dng trong mi trng oxi ho mnh.
Hp kim Ni-Cr
80% Ni, 20%Cr - Nimonic; Ni76Cr16Fe7 Inconel l nhng hp kim d dng b th
ng v c dng thay th thp khng g trong iu kin khng p ng yu cu chng n
mn.
Hp kim Ni-Mo
Hp kim Ni60Mo20Fe20 (Hastelloy A) v Ni65Mo30Fe5 (Hastelloy B) bn trong mi
trng HCl, H2SO4 60% mi nhit . Hp kim Ni59Mo17Cr14Fe6W5 (Hastelloy C) bn
trong mi trng oxi ha.

7.1.7 Nhm v hp kim nhm

Nhm nguyn cht

25oC th in cc tiu chun ca nhm EoAl3 +

= 1,66 V rt m nn khng bn nhit

Al

ng hc. Trong khng kh nhm c bo v nh mng oxit Al2O3 c dy khong 5 20

nm cho nn gi tr th in cc dng hn, v th nhm bn trong khng kh ngay c khi c
SO2, cng nh trong nc.
Th in cc ca nhm trong dung dch NaCl 3% bng 0,55 V.
Trong dung dch c pH > 4, ion Al3+ kt hp vi OH to ra Al(OH)3 kh tan v sau
chuyn thnh Al2O3.nH2O.

132

Khi tng pH ca mi trng Al c th b n mn v oxit nhm v hiroxit nhm l lng

tnh. S n mn nhm trong mi trng kim km theo s gii phng H2.
Al + 4OH U [Al(OH)4] + 3e

Phn ng anot:
Phn ng catot:

3H2O + 3e U

H2 + 3OH

Al + 3H2O + OH U [Al(OH)4] +

Phn ng tng cng:

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

a s hp kim nhm c tnh bn c hc cao v c s dng rt rng ri trong kin trc,

xy dng v cc ngnh cng ngh cao sn xut t, my bay, cc dng c nh bp. Trong
mi trng trung tnh, khi c mt ion Cl, hp kim nhm thng b n mn im.
Tr cc nguyn t Zn, Be, Mg, khi nhm tip xc vi cc nguyn t u to thnh pin
Ganvanic, khi nhm b ho tan. bn chng n mn ca hp kim nhm thay i trong
mt phm vi rng tu thuc vo thnh phn hp kim.
Hp kim nhm c k hiu gm 4 ch s (xem bng 7.2).
Bng 7.2. K hiu mt s hp kim nhm theo tiu chun Vit Nam
v tiu chun ca hip hi nhm (AA) ca M

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

(*) K hiu l 4 s (v d 1060)

Ch s u 1 l nhm Al nguyn cht
Ch s u 2 l hp kim cha nguyn t Cu l ch yu
Ch s u 3 l hp kim cha nguyn t Mn v Mn + Mg
Ch s u 4 l hp kim cha nguyn t Si
Ch s u 5 l hp kim cha nguyn t Si + Mg (nhiu) v Cr
Ch s u 6 l hp kim cha nguyn t Si + Mg l ch yu
Ch s u 7 l hp kim cha nguyn t Zn + Mg
Hp kim h Al-Cu in hnh l Dura c thnh phn %:
Cu4-Mg0,6-Mn0,6-SiFe0,7
Cc hp kim nhm rt nhy vi n mn khi c ti trng ng. V d vt liu hp kim
nhm ch to my bay, s c mt ca Mn c tc dng lm tng bn chng n mn hp kim
nhm.

7.2 X l mi trng bo v kim loi

7.2.1 Loi tr cc cu t gy n mn
Trong mi trng kh quyn, lm gim m l mt bin php hn ch s n mn c
hiu qu. Nu m tng i di 50% th tc n mn rt b. C th s dng cc cht
ht m silicagel lm kh khng kh. Ngoi ra vic loi tr cc tp cht gy n mn cng
cn thit. Trong khng gian bao kn (bao gi) cc cu kin c th dng cc cht c ch bay
hi hn ch tc n mn kim loi.
Lm nng khng kh trong khng gian cha cc cu kin cng l mt bin php gim
m.
Trong dung dch cht in li, s iu chnh pH v mi trng trung tnh hn ch s n
mn kim loi c th thc hin c mt cch d dng song vic loi tr oxi, tc nhn gy n
mn hon ton khng n gin.
ho tan ca oxi trong dung dch nc ph thuc vo nhit , vo p sut ring phn
PO2 v lng mui c trong dung dch. Khi nhit tng th p sut PO2 ho tan gim, lng
mui trong dung dch cng tng th hm lng oxi cng thp.
Vic loi tr oxi c th thc hin bng nhiu cch.

134

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.

7.2.2 S dng cht c ch bo v kim loi khi s n mn

Cht c ch l nhng hp cht v c hoc hu c m khi thm mt lng rt nh vo
mi trng n mn c tc dng km hm tc n mn kim loi.
Khi s dng cht c ch cn phi lu mt iu kin sau:
Cht c ch khng gy c hi cho con ngi v nhim mi trng;
Gi thnh thp.
Ngy nay c rt nhiu hp cht c tc dng km hm tc n mn song c th tm phn
chia thnh hai loi:
Cht c ch gy th ng;
Cht c ch hp ph.
a) Cht c ch gy th ng

Cht c ch gy th ng lm gim tc n mn kim loi do mi trng n mn gy ra

v phi p ng cc yu cu sau:
1) Khi c mt cht c ch trong mi trng n mn, gi tr th oxi ho kh Eredox ca h
cht c ch phi dng hn th th ng EP (xem hnh 7.1):
Eredox > EP

(7.2)

2) Gi tr mt dng catot ca h c ch redox iC(redox) ti th ti hn ECr phi ln hn

mt dng ti hn iCr (ng 1 trn hnh 7.1).

135

iC(redox) > iCr v im << iCr < iC(redox)

(7.3)

Nu cht c ch c nng cha km hm tc n mn kim loi (ng 2 trn

hnh 7.1) th kim loi vn b n mn.
lgi (A/cm 2 )
ic
lgi c(Redox)
1

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

V d cht c ch Na2Cr2O4 c dng chng n mn cho thp trong cc h thng

nc lm lnh.
trng thi th ng, trn mt kim loi thp tn ti oxit Cr2O3 do phn ng:
CrO24 + 10H + 6e Cr2O3 + 5H2O
+

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 Nng cao bn chng n mn kim loi bng cc lp sn ph

hn ch s ph hu kim loi, ngha l lm gim tc n mn kim loi do mi trng
gy ra n mc nh nht, c th s dng nhiu bin php khc nhau.
Ngn cch kim loi tip xc vi mi trng n mn bng cc lp ph l mt bin php c
hiu qu bo v chng n mn kim loi, sau y s cp n mt s lp ph.
7.3.1 Ph kim loi ln b mt kim loi
7.3.1.1. Ph bng phng php nhng vo kim loi nng chy

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

Bng phng php ph nng chy ny c th thu c lp ph bo v kh dy, c

bm dnh cao vi kim loi nn. i khi gia lp ph v kim loi nn c th to thnh hp
cht. Khng ph ch trc tip ln thp m dng hp kim ch - thic (20 25% Sn).
Ph km nng chy ln nn thp c p dng kh rng ri bo v chng n mn cho
thp. Lp km trn nn thp c tc dng trang tr cho p, song n ng vai tr l anot tan
bo v cho cc cu kin thp khng b n mn (tn lp nh l thp trng km).
Ph km ln b mt kim loi thp c tin hnh nh sau:
Vt c ph l thp c x l bng dung dch NH4Cl + ZnCl2 ho tan cc oxit, sau
em sy kh v tip theo sau l nhng vo km nng chy. Hoc c th nhng vt cn
c ph trc tip vo dung dch mui nng chy NH4Cl v ZnCl2 nm trn kim loi km
nng chy.
Dng kh amoniac ty sch lp oxit trn vt cn ph trc khi nhng vo km nng
chy. hiu chi tit v cng ngh ny hy tm ti liu v ph km nng.
7.3.1.2. M in

bo v kim loi (v d thp) khi s n mn ca mi trng gy ra ngi ta thng

m ln thp cc kim loi: Zn, Cd, Ni, Cu, Cr, Sn.
Nguyn tc m in

S hot ng ca mt b m in xy ra l mt qu trnh in phn, trong catot l vt

liu m, cn anot tan cung cp ion kim loi c kt ta trn cc m gip cho nng ion
kim loi trong dung dch cht in li t b bin i. V d trong qu trnh m km, anot km
ho tan cung cp ion km cho dung dch cht in li, hoc trong qu trnh m niken, anot
tan niken cung cp ion Ni2+ cho dung dch cht in li nh tc dng ca dng in mt chiu
bn ngoi t vo.
V d 1: M km trn kim loi en

Thnh phn dung dch m (g/l):

200 250 g/l

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

DC = 0,5 1 A/dm2, nhit phng.

Dung dch xianua c phn b cao, m cc chi tit phc tp, c th dng thay th bng
dung dch phc n amoniacat (g/l):
ZnO

12 15;

NH4Cl :

240 260

138

H3BO3 :

20 25;

gelatin :

12

DC = 0,8 1 A/dm2, pH = 7, nhit phng.

Sau khi m xong tin hnh th ng ha bng dung dch sau:
8 12 g/l;

H2SO4 :

Na2Cr2O7 :

150 200 g/l

Nhit 15 30oC, thi gian th ng 0,1 0,3 pht.

V d 2: M ng

M ng dng sunfat vi thnh phn sau:

CuSO4.5H2O :

200 300 g/l

50 70 g/l,

H2SO4 :

nhit 20 30oC v DC = 1 2 A/dm2, anot - Cu.

Qu trnh m ng ln nn st xy ra phn ng:
Fe + Cu2+ Cu + Fe2+
ng bm trn st dng xp, lp m khng bm dnh. Ngy nay ngi ta c th m ng
ln st trc tip bng cch cho thm cht hot ng b mt. u im ca dung dch ny l
khng c, khng gy nhim mi trng.
tng bm dnh ngi ta m ln st mt lp lt ng t dung dch xianua vi thnh
phn (g/l) sau:
T l CuCN/NaCN = 1/2 ng vi phc Na2[Cu(CN)2], CuCN 20 30, NaCN t do 5 10,
NaOH 5 10, DC = 0,2 2 A/dm2, to = 15 55oC, anot-Cu.
V d 3: M niken

Niken c in th dng hn so vi st, lp m niken trn st ng vai tr l catot v khi

xy ra hin tng n mn th st l anot. V vy, bo v st khng b n mn (ph tng xe
p, t, cc cu kin khc) th lp m niken phi ph trn st rt kn, cht st, c bm
dnh cao, lp m dy hoc lp m gm nhiu lp chng ln nhau.
C hai loi m niken:
+ M niken m vi thnh phn g/l sau:
NiSO4.7H2O - 230 300
H3BO3 - 35
NaCl - 15 40
pH = 3 5
DC = 0,8 2,5A/dm2
to = 25 30oC
Anot - Ni
C th m to lp niken c chiu dy 15 25m.
+ M niken bng trc tip vi thnh phn g/l nh sau:

139

NiSO4.7H2O - 260 300

H3BO3 - 30 35
NiCl2.6H2O - 40 60 vi cht lm bng v san nn 1,4-butyliol 0,12 0,16 g/l, saccarin
0,7 1,3 g/l, ftalimid 0,08 0,1g/l, DC = 1 2 A/dm2, to = 45 50oC, anot - Ni, khuy lin tc,
thng xuyn phi lm sch dung dch.
Ta c th m niken bng phng php ho hc theo phn ng sau:
NiCl2 + 2NaH2PO2 + 2H2O Ni + 2NaH2PO3 + 2HCl + H2
B mt vt m cn phi c hot ho trc khi m, lp m ny c cng cao v trong
lp niken c ln phtpho (3 15%). M niken ho hc c th m ln nn st hoc cc cht
do, thu tinh.
V d 4: M crom

Dung dch m crom c thnh phn sau:

CrO3 - 250 g/l
H2SO4 - 2,5 g/l
DC = 30 80 A/dm2
to = 40 70oC
Anot - Pb
iu chnh mt dng thu c lp m c tnh cht c hc khc nhau.
bo m lp m kn trn nn st, c kh nng chng n mn cao v trang tr p, vi
mu trng nh xanh ngi ta thng m nhiu lp. V d m trn nn st cc lp theo th t
sau: Fe, Cu, Ni, Cr hoc Fe, Ni (m), Ni (bng), Cr (bng) vi chiu dy lp m Cr 0,5 m.
Lp m crom c hiu sut thp v c kh c bay ln, cn phi c thit b an ton lao
ng.

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

C cc phn ng thu phn:

nc nng

ZZZZZZZ
X
Mn(H2PO4)2 YZZZZZZ
Z MnHPO4 + H3PO4

3MnHPO4

nc nng

ZZZZZZZ
X
YZZZZZZ
Z 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).
7.3.2.2

Oxi ha in ha kim loi

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

Hnh 7.2. S to mng oxit nhm

1. Mng pha trong; 2. Mng pha ngoi

141

Qu trnh oxi ho nhm c thc hin trong dung dch sau:

H2SO4 20%, mt dng anot Da = 1 2 A/dm2, to = 20oC.
tng kh nng bo v ca mng, sau khi ra sch mng bng nc nng, hi nc, c
th tin hnh cromat ho hoc nhum mu.
Mng oxit nhm cng to c bng phng php ho hc vi dung dch sau (g/l):
Na2CO3 - 50, NaOH - 2,5, Na2CrO4 - 15, to = 90 95oC, thi gian 5 10 pht, mng
mng (3 4 m), bn c hc km.
Oxi ha ha hc thp

Thnh phn dung dch (g/l):

NaOH - 600 700, NaNO2 - 200 250, NaNO3 - 50 100, thi gian 30 90 pht to =
135 145oC. Lp oxit c thnh phn ch yu: Fe3O4 dy 0,6 3 m.
Sau khi oxi ha nhng trong nc x phng 2 3% trong 2 3 pht, tip theo nhng
trong du bin th 5 10 pht 105 120oC.
Oxi ho in ho thp

Ch lm vic: dung dch NaOH 40%, to = 80 120oC,

Da = 3 10
A/dm2. Nhum mu oxi ha en ch yu trang tr to mu en cho cc dng c chnh xc.

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

Cht kt dnh ng rn do b oxi ha trong mi trng khng kh.

Sn du thng l cc loi du thc vt: du lanh, du tng, du u tng.
Nha alkyt l este ca diaxit v ru a chc. Vi d axit phtalic (HOOC
C2H4COOH) v glyxerin.
+ Cht kt dnh ng rn do bc hi dung mi: polymethylmethacrylat.
+ Cht kt dnh ng rn do polymer ha: nha epoxi, nha polyurethan
b) Pha rn: Cc loi pigment v cht n.

Sc t chng n mn: bt km, bt ch, Pb3O4, ZnCrO4.

Sc t gim thm nc: ZnO, TiO2, Fe2O3, graphit.
Cht n: SiO2, SbSO4, bt tan, mica, CaCO3...
(Chi tit vn ny xin tham kho sch chuyn v sn ph.)

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.

7.4 Bo v kim loi chng n mn kim loi bng phng php in ho

Nguyn tc ca phng php in ho bo v chng n mn kim loi l dch chuyn th
v pha m nm trong min th loi tr n mn bng phng php phn cc bi dng ngoi
hoc t phn cc ca s khp kn pin n mn. Mt khc, c th to lp th ng trn mt kim
loi bng s phn cc anot. Phng php bo v ny thng c dng bo v nhng phn
kim loi tip xc vi mi trng dn in. V d trong nc bin, nc ven bin hoc trong
nc, trong t.
Da vo nguyn tc trn c hai phng php bo v in ho:
bo v catot bng dng ngoi dch chuyn th n mn v pha m ko theo s gim
dng n mn (xem hnh 7.3) n cc tiu.
bo v catot bng anot hy sinh, ni kim loi cn bo v vi kim loi khc c in th
m hn v th kim loi cn bo v c dch chuyn v pha m ko theo s gim tc n
mn.

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

Khi dch chuyn th v pha m t O n O2 th dng n mn gim t O1 O. Khi

trn st im 0 v ch c s thot kh H2 theo phn ng:
2H+ + 2e H2
Th gii hn Egh, ti s n mn st t cc tiu v nu dch chuyn th m hn Egh th
kh H2 trn st thot ra vi tc ln, s hiro kim loi lm gim bn c hc ca st.

7.4.1 Phng php bo v catot bng dng ngoi

Kim loi cn c bo v, cc ng ng dn nhin liu di t, v tu bin c ni
vi cc m ca ngun in mt chiu, cn cc dng ca ngun in ni vi mt anot bng
vt liu t tan (xem hnh 7.4).

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.

7.4.2 Bo v bng anot hy sinh

Kim loi cn c bo v phi c gi tr in th dng hn vt liu lm anot hy sinh.
Anot hy sinh b ho tan bo v kim loi.
Cng trnh c bo v thng lm bng thp. V d v tu bin, cc gin khoan khai
thc du kh ngoi bin. Trong trng hp vt liu lm anot hy sinh l cc kim loi nhm,
km, magie hoc hp kim ca chng.
Hp kim nhm ch dng trong mi trng m nhm d b ho tan, v d trong nc bin.
S bo v chng n mn kim loi bng anot hy sinh c trnh by trn hnh 7.5.

145

Hnh 7.5
S bo v chng n mn kim loi bng anot hy sinh

1. Thit b cn bo v; 2. Anot hy sinh; 3. Cht bc anot hy sinh;

4. Thit b kim tra; 5. Cng tc ng, ngt mch
iu kin anot hy sinh lm vic c hiu qu:
Gia vt bo v v anot hy sinh c hiu in th ln, ngha l anot hy sinh phi c
in th m hn in th ca thit b c bo v.
Vt liu anot c in th lm vic t thay i.
Vt liu anot phi c dung lng cao, n nh, khng b th ng trong mi trng lm
vic, n mn u, hiu sut cao (xem bng 7.3).
Mt dng bo v ph thuc vo s chnh lch in th ga anot hy sinh v vt bo v,
in tr ring ca mi trng. i vi cc loi t c in tr ring khong 10 250 th
thng dng anot hy sinh Mg.
Bng 7.3. Cc thng s k thut ca 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

Trong nc ngt in tr ring khong 10 30 th c th dng loi anot hy sinh Mg,

Zn.
Trong nc bin in tr ring khong 0,2 0,7 th dng ch yu l anot hy sinh Al v
Zn.
Vic lp t anot hy sinh c nhiu cch v tu thuc vo tng trng hp c th.
Trong mi trng nc bin dn in tt thng gn trc tip vo b mt kim loi cn
bo v (v tu bin).

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

Phn loi bn chng Ch s

n mn
Pmm/nm
Siu bn
bn cao

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

nh gi mt cch nh lng v phn loi bn chng n mn theo tiu chun xc

nh (xem bng 8.1), vic xc nh tc n mn kim loi c th s dng cc phng php
sau:
Phng php trng lng.

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.

8.2 Cc phng php xc nh tc n mn kim loi

8.2.1 Phng php trng lng

Tc n mn kim loi do mi trng gy ra c xc nh bng phng php trng

lng, ngha l tnh theo lng kim loi (tnh theo gam) b mt i ng vi mt n v thi
gian v n v din tch mu (v n v theo quy c) theo cng thc sau:
=

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)

Cng thc (8.1) thng p dng cho trng hp n mn u.

Phng php ny thng gp nhng sai s do php cn gy ra, v th phi dng cn phn
tch c chnh xc cao. Ngoi ra vic chun b mu trc v sau khi th nghim cng ng
mt vai tr rt quan trng.
Cc mu trc khi th nghim phi c lm sch ht cc lp g, mi nhn sao cho din
tch thc phi gn bng din tch hnh hc S. Trc khi nhng mu vo mi trng n mn b
mt mu c lm sch ht du m bng cn hoc bng dung mi axeton bo m b mt
hon ton thm t, sy kh v em cn ta c trng lng mo.
Sau thi gian t th nghim trng thi b mt mu kim loi b thay i, hoc to thnh cc
lp g. V th cn phi lm sch cc sn phm n mn, song trnh s ho tan kim loi (s
dng cc TCVN hoc ASTM bit cch x l b mt). B mt kim loi sau khi c lm
sch sn phm cng phi x l bng cc dung mi hu c, sy kh v em cn thu c m1.
Sau tnh tc n mn theo cng thc (8.1).
Nu gi tr m qu nh th php o thng d gp sai s ln, trong trng hp cn
phi lm th nghim nhiu ln ly gi tr trung bnh hoc ko di thi gian th nghim.
nh gi tc n mn theo tn tht chiu su P (chiu dy ca kim loi b hao ht) tnh
theo cng thc:
=

(8.3)

149

trong : P - chiu dy b n mn (mm, cm);

d - khi lng ring ca kim loi (g/cm3);
- tc n mn (mg/dm2. ngy m).

n v o:
[P] = l/t

(8.4)

trong : l - chiu di (mm, cm);

t - thi gian, thng tnh theo nm.
Nu chn [P] = mm/nm, [] = mg/dm2.ngy m v [d] = g/cm3 th quan h gia chng
c tnh theo cng thc:
=

.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)

8.2.2 Phng php th tch

S n mn in ho lun lun c hai phn ng gn lin vi nhau, l s ho tan kim
loi (ti anot) v km theo phn ng gii phng hiro hoc tiu th oxi trn catot ca pin n
mn.
V vy, ngoi vic dng phng php trng lng nh gi tc n mn bng s hao
tn trng lng cn c th nh gi tc n mn thng qua th tch ca hiro c gii
phng ra hoc th tch oxi b tiu th.

8.2.2 Cc phng php phn tch

xc nh tc n mn kim loi ngi ta xc nh nng ion kim loi b ho tan
vo mi trng xm thc, t suy ra tc n mn. C th dng cc phng php phn tch
nh lng, v d phng php quang ph, phng php hp ph nguyn t, phng php cc
ph,

8.2.3 Phng php in ho

Mt u im quan trng ca phng php in ho l cho php xc nh c tc n
mn kim loi trong mt thi gian ngn v chnh xc vi iu kin th nghim c tin hnh
mt cch thn trng v ng quy cch. C th dng phng php o in ho xc nh tc
n mn kim loi trong iu kin gia tc so snh vi nhng th nghim trong iu kin t
nhin. Phng php ny s em li kt qu kh ph hp vi iu kin t nhin nu chn dung
dch v iu kin m phng phn nh c nhng yu t gn st thc t hin trng. Trong
trng hp ngc li, nu iu kin o in ho khng ph hp vi iu kin thc s gy ra
s sai st trm trng.
Trong qu trnh n mn kim loi xy ra ch gn vi s kh ion H+ trong dung dch hoc
l s tiu th oxi trong dung dch, th vic o in ho s em li cc kt qu kh ph hp vi
iu kin thc t.

150

8.3.2.1 o in th n nh, in th oxi ho kh ca dung dch

o in th n nh hoc in th n mn Em l mt php o n gin nht. N khng

em li thng tin v tc n mn nhng cho php d on v qu trnh khng ch s n
mn, qu trnh catot hoc anot (xem hnh 8.1, 8.2).
Nu th n mn Em dch chuyn v pha dng th khi qu trnh anot b km hm v
qu trnh catot tr nn d dng hn.
Nu in th dch chuyn v pha m hn th qu trnh anot din ra d dng hn hoc qu
trnh catot b km hm.
3

5
1

Ea

2
thi gian (t)

Hnh 8.1

Hnh 8.2.

S o th n nh (th n mn Em) ph thuc thi gian.

Em - f(t)

S bin i th n mn theo thi gian Em - f(t)

1 - in cc lm vic (WE)
2 - in cc so snh (RE) - in cc bc
7

3 - Von k c R ln hn 10

1 - in th n mn dch chuyn v pha dng (phn

cc anot)
2 - in th n mn dch chuyn v pha m phn cc
catot)

4 - Dung dch nghin cu

5 - Cu ni cha KCl (hoc HCl)

So snh gi tr th n mn Em o c vi gi tr th trn th in th (E) v pH ca

Pourbaix suy on kh nng xy ra n mn trn in cc nghin cu.
o in th oxi ho kh ca mi trng bng cch nhng dy Pt vo mi trng v ghp
vi in cc so snh (in cc bc) to ra pin in v o sut in ng ca pin. Tnh in th
oxi ha kh suy ra kh nng gy ra n mn hoc to ra th ng.
8.3.2.2 o ng cong phn cc - s ph thuc ca mt dng in i vo in th E

Php o ng cong phn cc c th xem l m rng php o in th n mn Em m

khng c dng phn cc t dng ngoi (I = 0). Vy vic o ng phn cc c th thc hin
bng hai cch:
p dng ngoi I 0 o th, ngha l t vo h mt gi tr mt dng khng i (I =
const) v o gi tr th E t trng thi n nh v to ra mt s ph thuc ca mt dng
vo th. Phng php gi l phng php dng tnh (Galvanostatic).
p mt gi tr th khng i t ngun in bn ngoi nh mt my pht th n nh
(Potentiostatic, E = const) o gi tr dng I khi t trng thi n nh v to ra s ph thuc
ca dng vo th hoc th vo dng v c gi l ng phn cc.

151

1. o ng cong phn cc theo phng php dng tnh (Galvanostatic)

C th dng thit b o Potentio-Galvanostatic thay cho cc cm thit b gm cc phn (8,

7, 6, 5) trn hnh v, phn cn li ba in cc 1, 2, 4 ni vo my o Potentio-Galvanostatic
v tin hnh o.
Nhng iu cn ch trong php o:
Chun b dung dch sch, t cc in cc 1 v 2 i din nhau.
Khong cch gia in cc 1 v 4 phi rt gn nhau
B mt in cc nghin cu, in cc 1 phi c din tch chnh xc (kim loi c trong
nha epoxi c mt mt lm vic vi din tch thng l 1 cm2, phn cn li b che ph cch
in), c lm nhn vi bng cao v x l thm t hon ton trc khi tin hnh o.
Chn khong th ph hp, t php o thu c s liu in th ng vi thay i gi tr
mt dng i, sau v ng phn cc dng i - f(E) hoc E - lgi (xem hnh 8.4 v 8.5).
S thit b o ng phn cc theo phng php dng tnh c trnh by trn hnh
(8.3).
8
6

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)

2. o ng cong phn cc theo phng php th tnh (Potentiostatic)

S o ng cong phn cc theo phng php th tnh c trnh by trn hnh (8.6).

153

Bng thit b Potentiostat (7) duy tr gi tr th khng i trn in cc lm vic (1) - WE

so vi in cc so snh (2) RE, p ln in cc lm vic nhng gi tr th in cc khc
nhau v ghi li cc gi tr dng tng ng.
T cc gi tr thc nghim o cc gi tr dng i ph thuc in th E cho php v ng
phn cc i - f(E) (xem hnh 8.4) hoc E - lgi (xem hnh 8.5). T cc th trn cc hnh 8.4 v
8.5 cho php xc nh th n mn Em v im ca h kho st.
Mt u im quan trng ca phng php th
tnh l trn ng phn cc i - f(E) c xut hin
min th ng. iu ny rt quan trng i vi vic
nghin cu kh nng th ng ca cc hp kim, kh
nng to th ng ca cc h cht oxi ho kh thm
vo dung dch. Phng php ny rt tin li cho
vic nghin cu nh gi tc n mn, kh nng
c ch ca cc cht c ch i vi thp trong mi
trng kim cng nh gn trung tnh.
Cn phi lu rng phng php ngoi suy cc
ng Tafel ca hai phng php trn tnh gi tr
Em v im ch chnh xc i vi h n mn ch c
hai h oxi ho kh (s ho tan kim loi v s kh
hiro hoc l oxi).
Trong iu kin n mn xy ra c s phn cc
nng th php ngoi suy s khng cn chnh xc
na. V d vic o phn cc catot v anot ca kim
loi trong mi trng axit yu nh gi tc n
mn c tin cy km.

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

8.3.2.3 Phng php o in tr phn cc

Phng php o in tr phn cc cn c gi l phng php phn cc tuyn tnh.

Phng php ny do Stern Geary ra nm 1956 v c pht trin, p dng tnh tc
n mn cho nhiu h n mn c kt qu rt tt.
Trn ng phn cc E - f(i) p dng cho h n mn c hai phn ng (xem hnh 8.7).
Phn ng xy ra trn anot, kim loi Me b ho tan:
Me ze Mez+

(8.7)

v trn catot xy ra phn ng:

zH+ + ze

z
2

H2

(8.8)

Ti khong th phn cc E rt nh so vi Em, E = 10 mV, s ph thuc ca E vo

mt dng (th nghim vi in cc c din tch 1 cm2) l tuyn tnh:

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)

Mt khc gi tr B ca (8.9) c tnh theo cng thc:

=

b .be

2,3. ( b + be )

(8.10)

trong : bH - l h s dc on thng Tafel i vi qu trnh catot thot kh hiro thay i

gi tr t 0,06 V ; bMe - l h s dc on thng Tafel i vi qu trnh anot ho tan
kim loi thay i t 0,06 0,12 V.
T (8.9) ta c:
im =

Rp

(8.11)

Vy mun xc nh tc n mn kim loi theo mt dng n mn im ta phi xc nh

B da trn cc gi tr h s dc (xc nh bng thc nghim t hnh 8.5) ca cc ng
Tafel catot v anot theo (8.10) v xc nh Rp - in tr phn cc.
Xc nh Rp theo th (8.7), Rp chnh l tg.
Rp = tg

(8.12)

Phng php o Rp tnh dng n mn im s chnh xc nu Rp >> R (R - in tr ca dung

dch). Mt cch gn ng chp nhn gi tr B trong (8.1) bng 0,026.
Da vo gi tr Rp nh gi bn chng n mn vt liu.
V d i vi ct thp btng, nu Rp < 50 k.cm2 th n bt u b n mn. Rp < 20
k.cm2 ct thp b n mn nghim trng.

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

Sr(OH)2.8H2O + 2e = Sr + 2OH + 8H2O

2,990

Ba(OH)2.8H2O + 2e = Ba + 2OH + 8H2O

2,097

H2O + e = H(r.) + 2OH

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

ThO2 + 2H2O + 4e = Th + 4OH

2,640

18

Sc(OH)3 + 3e = Sc + 3OH

2,600

19

HfO(OH)2 + H2O + 4e = Hf + 4OH

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

H2 AlO3 + H2O + 3e = Al + 4OH

2,350

29

Mg2+ + 2e = Mg

2,340

30

H2ZrO3 + H2O + 4e = Zr + 4OH

2,320

31

Am3+ + 3e = Am

2,320

32

Al(OH)3 + 3e = Al + 3OH

2,310

33

Be2O32 + 3H2O + 4e = 2Be + 6OH

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

ThO2 + 4H+ + 4e = Th + 2H2O

1,80

47

H2BO3 + H2O + 3e = B + 4OH

1,79

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

53

HfO2+ + 2H+ + 4e = Hf + H2O

1,68

54

Al3+ + 3e = Al

1,67

55

HPO32 + 2H2O + 2e = H2PO2 + 3OH

1,65

56

Na2UO4 + 4H2O + 2e = U(OH)4 + 2Na+ +4OH

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

ZnO2 + 4H+ + 4e = Zr + 2H2O

1,43

62

2SO32 + 2H2O + 2e = S2O42 + 4OH

1,40

63

UO2 + 4H+ + 4e = U + 2H2O

1,40

64

As + 3H2O + 3e = AsH3 + 3OH

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

[Cr(CN)6]3+ e(trong dd KCN) = [Cr(CN)6]4

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

H2GaO3 + H2O + 3e = Ga + 4OH

72

ZnO22 + 2H2O + 2e = Zn + 4OH

73

CrO2 + 2H2O + 3e = Cr + 4OH

74

SiF62 + 4e = Si + 6F

75

1,22
1,216
1,20

1,20

TiF62 + 4e = Ti + 6F

1,19

76

In2O3 + 3H2O + 6e = 2In + 6OH

1,18

77

V2+ + 2e = V

1,18

78

3
16H2O + HV6O17
+ 30e = 6V + 33OH

1,15

79

N2 + 4H2O + 4e = N2H4 + 4OH

1,15

80

HCOO (A) + 2H2O + 2e = HCHO(A) +3OH

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

PO34 + 2H2O + 2e = PO32 + 3OH

1,05

160

STT

Phn ng in cc

Eo(V)

87

N2O + 5H2O + 4e = 2NH2OH + 4OH

1,05

88

MoO24 + 4H2O + 6e = Mo + 8OH

1,05

89

WO24 + 4H2O + 6e = W + 8OH

1,05

90

Tl2S + 2e = 2Tl + S2

1,04

91

[Zn(NH3)4]2+ + 2e = Zn + 4NH3 (A)

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

CNO + H2O + 2e = CN + 2OH

0,96

96

Sn ( OH )6 + 2e = HSnO2 + 3OH + 2H2O

0,96

97

Pu(OH)4 + e = Pu(OH)3 + OH

0,95

98

TiO2 (v nh hnh) + 4H+ + 4e = Ti +2H2O

0,95

99

Cu2S + 2e = 2Cu + S2

0,95

100

CO32 + 2H2O + 2e = HCO2 + 3OH

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

SO24 + H2O + 2e = SO32 + 2OH

0,90

106

Cr2+ + 2e = Cr

0,90

107

HGeO3 + 2H2O + 4e = Ge + 5OH

0,88

108

P + 3H2O + 3e = PH3 + 3OH

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

2NO3 + 2H2O + 2e = N2O4 + 4OH

0,85

113

SiO2 + 4H+ + 4e = Si + 2H2O

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

Ta2O5 + 10H+ + 10e = 2Ta + 5H2O

0,81

121

CdCO3 + 2e = Cd + CO32

0,80

122

ZnSO4.7H2O + 2e = Zn(amagam) + SO24 + 7H2O

0,799

123

HSnO2 + H2O + 2e = Sn + 3OH

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

H3BO3 + 3H+ + 3e = B + 3H2O

0,73

133

N2O22 + 6H2O + 4e = 2NH2OH + 6OH

0,73

134

Cr3+ + 3e = Cr

0,71

135

Ag2S + 2e = 2Ag + S2

0,71

136

AsO34 + 2H2O + 2e = AsO2 + 4OH

0,71

137

HgS + 2e = Hg + S2

0,70

138

[Mn(CN)6]3 + e = [Mn(CN)4]2 + 2CN

0,70

139

Te + 2H+ + 2e = H2Te

0,70

140

Ni(OH)2 + 2e = Ni + 2OH

0,69

141

AsO2 + 2H2O + 3e = As + 4OH

0,68

142

Ag2S + H2O + 2e = 2Ag + OH + SH

0,67

143

Fe2S3 + 2e = 2FeS + S2

0,67

144

SbO2 + 2H2O + 3e = Sb + 4OH

0,66

145

TlBr + e = Tl + Br

0,658

146

Ga3+ + e = Ga2+

0,65

147

CoCO3 + 2e = Co + CO32

0,632

148

Nb2O5 + 10H+ + 10e = 2Nb + 5H2O

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

Re O4 + 2H2O + 3e = ReO2 + 4OH

0,594

155

H3PO3 + 2H+ + 2e = H3PO2 + H2O

0,59

156

HCHO(A) + 2H2O + 2e = CH3OH(A) +2OH

0,59

157

Re O4 + 4H2O + 7e = Re + 8OH

0,584

158

NO3 + NO + e = 2NO2

0,58

159

2SO3 + 3H2O + 4e = S2O32 + 6OH

0,58

160

CuS + 2e = Cu2S + S2

0,58

161

PbO + H2O + 2e = Pb + 2OH

0,578

162

ReO2 + H2O + 4e = Re + 4OH

0,576

163

TeO32 + 3H2O + 4e = Te + 6OH

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

HPbO2 + H2O + 2e = Pb + 3OH

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

H3PO3 + 2H+ + 2e = H3PO2 + H2O

0,50

181

2CO2 + 2H+ + 2e = H2C2O4 (A)

0,49

182

H3PO3 + 3H+ + 3e = P + 3H2O

0,49

183

[Ni(NH3)6]2+ + 2e = Ni + 6NH3 (A)

0,48

184

NO2 + H2O + e = NO + 2OH

0,46

185

BiOOH + H2O + 3e = Bi + 3OH

0,46

186

ClO3 + H2O + e = ClO2 (k) + 2OH

0,45

187

NiCO3 + 2e = Ni + CO32

045

188

In3+ + e = In2+

0,45

189

Fe2+ + 2e = Fe

0,441

190

CdSO4. 3H2O + 2e = Cd + SO24 +

191

Eu3+ + e = Eu2+

0,43

192

[Cu(CN)2] + e = Cu + 2CN

0,43

193

[Co(NH3)6]2+ + 2e = Co + 6NH3 (A)

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

Ga2O + 2H+ + 2e = 2Ga + H2O

0,40

199

Hg ( CN )4 + 2e = Hg + 4CN

0,37

200

Ti3+ + e = Ti2+

0,37

201

ScO32 + 3H2O + 4e = Sc + 6OH

0,366

202

PbI2 + 2e = Pb + 2I

0,365

203

Cu2O + H2O + 2e = 2Cu + 2OH

0,361

204

Se + 2H+ + 2e = H2Se

0,36

205

Hg2(CN)2 + 2e = 2Hg + 2CN

0,36

206

PbSO4 + 2e = 2Hg + 2CN

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

PtS + 2H+ + 2e = Pt + H2S

0,30

213

[Ag(CN)2] + e = Ag + 2CN

0,361

214

NO3 + 5H2O + 6e = NH2OH + 7OH

0,30

215

PbBr2 + 2e = Pb + 2Br

0,280

216

Co2+ + 2e = Co

0,277

217

H3PO4 + 2H+ + 2e = H3PO3 + H2O

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

CuS + 2H+ + 2e = Cu + H2S

0,259

222

V3+ + e = V2+

0,255

223

Sb2O3 + 6H+ + 6e = 2Sb + 3H2O

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

CH3OH (A) + H2O + 2e = CH4 + 2OH

0,25

228

HO2 + H2O + e = OH + 2OH

0,24

229

2H2SO3 + H+ + 2e = HS2O4 + H2O

0,23

230

N2 + 5H+ + 4e = N2H5+

0,23

231

Cu(OH)2 + 2e = Cu + 2OH

0,23

232

2SO24 + 4H + 2e = S2O62 + 2H2O

0,224

233

Mo3+ + 3e = Mo

0,2

234

CuI + e = Cu + I

0,187

235

2NO3 + 2H2O + 4e = N2O42 + 4OH

0,180

236

PbO2 + 2H2O + 4e = Pb + 4OH

0,16

237

AgI + e = Ag + I

0,151

238

GeO2 + 4H+ + 4e = Ge + 2H2O

0,15

1
2

0,27

(CN)2 + H2O

167

STT

Phn ng in cc

Eo(V)

239

Sn2+ + 2e = Sn

0,140

240

CO2 + 2H+ + 2e = HCOOH (A)

0,14

241

CH3COOH(A) + 2H+ +2e = CH3CHO(A) + H2O

0,13

242

Pb2+ + 2e = Pb

0,126

243

CrO24 + 4H2O + 3e = Cr(OH)3 + 5OH

0,12

244

[Cu(NH3)2]+ + e = Cu + 2NH3

0,11

245

2Cu(OH)2 + 2e = CuO + H2O + 2OH

0,09

246

WO3 + 6H+ + 6e = W + 3H2O

0,09

247

O2 + H2O + 2e = HO2 + OH

0,076

248

N2O + H2O + 6H+ + 4e = 2NH3OH+

0,05

249

[Cu(NH3)4]2+ + 2e = Cu + 4NH3 (A)

0,05

250

Tl(OH)3 + 2e = TlOH + 2OH

0,05

251

MnO2 + H2O + 2e = Mn(OH)2 + 2OH

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

RuO2 + 2H2O + 4e = Ru + 4OH

0,04

258

Fe3+ + 3e = Fe

0,036

259

Ag2S + 2H+ + 2e = 2Ag + H2S

0,036

260

TeO24 + 3H2O + e = Te + 6OH

0,02

168

STT

Phn ng in cc

Eo(V)

261

HCOOH(A) + 2H+ + 2e = HCHO(A) + H2O

0,01

262

2D+ + 2e = D2

0,0034

263

H2MoO4 (A) + 6H+ + 6e = Mo + 4H2O

0,0

264

CuI2 + 2e = Cu + 2I

0,0

265

[Cu(NH3)4]3+ + e = [Cu(NH3)2]+ + NH3 (A)

0,0000

266

2H+ + 2e = H2

0,0000

267

[Ag(S2O3)2]3 + e = Ag + 2S2O32

0,01

268

NO3 + H2O + 2e = NO2 + OH

269

HOsO5 + 4H2O + 8e = Os + 9OH

0,02

270

[Fe(C2O4)3]3 + e = [Fe(C2O4)2]2 + C2O42

0,02

271

SeO24 + H2O + 2e = SeO32 + 2OH

0,03

272

CuBr + e = Cu + Br

0,033

273

Rh2O3 + 3H2O + 6e = 2Rh + 6OH

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

PbS + 2H+ + 2e = Pb + H2S

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

HgO + H2O + 2e = Hg + 2OH

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

N2H4 + 4H2O + 2e = 2NH4OH + 2OH

0,1

286

Ir2O3 + 3H2O + 6e = 2Ir + 6OH

0,1

287

[Co(NH3)6]3+ + e = [Co(NH3)6]2+

0,1

288

2NO + 2e = N2O22

0,1

289

TiO2+ + 2H+ + e = H2O + Ti3+

0,1

290

Mn(OH)3 + e = Mn(OH)2 + OH

0,1

291

Hg2O + H2O + 2e = 2Hg + 2OH

0,123

292

CuCl + e = Cu + Cl

0,124

293

C + 4H+ + 4e = CH4

0,13

294

Hg2Br2 + 2e = 2Hg + 2Br

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

2NO2 + 3H2O + 4e = N2O + 6OH

0,15

300

Sb2O3 + 6H+ + 6e = 2Sb + 3H2O

0,152

301

BiCl4 + 3e = Bi + 4Cl

0,16

302

Pt(OH)2 + 2e = Pt + OH

0,16

303

BiOCl + 2H+ + 3e = Bi + 3H2O + Cl

0,16

304

Cu2+ + e = Cu+

0,167

305

S4 O62 + 2e = 2S2O32

0,17

170

Eo(V)

STT

Phn ng in cc

306

ClO4 + H2O + 2e = ClO3 + 2OH

307

CuCl2 + e = Cu + 2Cl

0,19

308

Ag4[Fe(CN)6] + 4e = 4Ag + [Fe(CN)6]4

0,194

309

SO24 + H + 2e = H2SO3 + H2O

0,20

310

S2O62 + 4H + 2e = 2H2SO3

0,20

311

2SO24 + 4H + 2e = S2O62 + H2O

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

Hg2(NCS)2 + 2e = 2Hg + 2NCS

0,22

317

(CH3)2SO2 + H+ + 2e = (CH3)2SO + 2H2O

0,23

318

H3AsO3 (A) + 3H+ + 3e = As + 3H2O

0,24

319

HCHO (A) + 2H+ + 2e = CH3OH (A)

0,24

320

Hg2Cl2 + 2e = 2Hg + 2Cl

0,244

321

HAsO2 (A) + 3H+ + 3e = As + 2H2O

0,247

322

PbO2 + H2O + 2e = PbO + 2OH

0,25

323

Pb3O4 (A) + H2O + 2e = 3PbO + 2OH

0,25

324

ReO2 + 4H+ + 4e = Re + 2H2O

0,252

325

IO5 + 3H2O + 6e = I

326

PuO2(OH)2 + e = PuO2OH + OH

0,26

327

Hg2Cl2 + 3e = 2Hg + 2Cl (aCl = 1)

0,267

+ 6OH

0,17

0,26

171

STT

Phn ng in cc

Eo(V)

328

Hg2Cl2 + 2e = 2Hg + 2Cl (trong KCl)

0,283

329

[Ag(SO3)2]3 + e = Ag + 2SO32

0,230

330

VO2+ + 2H+ + e = V3+ + H2O

0,314

331

BiO+ + 2H+ + 3e = Bi + H2O

0,32

332

Hg2CO3 + 2e = 2Hg + CO32

0,32

333

UO32+ + 2 e = UO2

0,33

334

(CN)2 + 2H+ + 2e = 2HCN

033

335

UO22+ + 4H + 2e = U

0,334

336

Hg2Cl2 + 2e = 2Hg + 2Cl

0,336

337

Ag2O + H2O + 2e = 2Ag + 2OH

0,344

338

Cu2+ + 2e = Cu

0,345

339

ClO3 + H2O + 2e = ClO2 + 2OH

340

Fe ( CN )6 + e = Fe ( CN )6

0,36

341

Hg2(CH3COO)2 + 2e = 2Hg + 2CH3COO

0,36

342

AgIO3 + e = Ag + IO3

0,37

343

Ti3+ = Ti4+ + e

0,37

344

[Ag(NH3)2]+ + e = Ag + 2NH3 (A)

0,373

345

HgCl24 + 2e = Hg + 4Cl

0,38

346

Hg(IO3)2 + 2e = Hg + 2IO3

0,40

347

2H2SO4 + 6H+ + 8e = 5H2O + S2O32

0,40

348

U6+ + 2e = U4+

0,4

349

TeO24 + H2O + 2e = TeO32 + 2OH

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

Hg2C2O4 + 2e = 2Hg + C2O42

0,417

354

NH2OH + 2H2O + 2e = NH4OH + 2OH

0,42

355

H2N2O2 + 6H+ + 4e = 2NH3OH+

0,44

356

RhCl36 + 3e = Rh + 6Cl

0,44

357

Ag2CrO4 + 2e = 2Ag + CrO24

0,446

358

2BrO + 2H2O + 2e = Br2 + 4OH

0,45

359

H2SO3 + 4H+ + 4e = S + 3H2O

0,45

360

Ag2C2O4 + 2e = 2Ag + C2O42

0,47

361

Ag2CO3 + 2e = 2Ag + CO32

0,47

362

4H2SO3 + 4H+ + 6e = 6H2O + S4 O62

0,48

363

Sb2O5 + 2H+ + 2e = Sb2O4 + H2O

0,48

364

PdI62 + 2e = PdI24 + 2I

365

Ag2MoO4 + 2e = 2Ag + MoO24

0,49

366

NiO2 + 2H2O + 2e = Ni(OH)2 + 2OH

0,49

367

IO + H2O + 2e = I + 2OH

0,49

368

AuI + e = Au + I

0,50

369

AuO2 + 2H2O + 3e = Au + 4OH

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

C2H4 + 2H+ + 2e = C2H6

0,52

373

2ClO + 2H2O + 2e = Cl2 + 4OH

0,52

374

Cu+ + e = Cu

0,522

375

TeO2 + 4H+ + 4e = Te + 2H2O

0,529

376

Ag2WO4 + 2e = 2Ag + WO24

0,53

377

I2 + 2e = 2I

0,534

378

I3 + 2e = 3I

379

BrO3 + 2H2O + 4e = BrO + 4OH

0,54

380

MnO4 + e = MnO24

0,54

381

Hg2CrO4 + 2e = 2Hg + CrO24

0,54

382

AgBrO3 + e = Ag + BrO3

0,55

383

H3AsO4 + 2H+ + 2e = H3AsO3 + H2O

0,559

384

TeOOH + 3H+ + 4e = 2H2O + Te

0,559

385

IO3 + 2H2O + 4e = IO + 4OH

0,56

386

Cu2+ + Cl + e = CuCl

0,56

387

AgNO2 + e = Ag + NO2

0,564

388

Te4+ + 4e = Te

0,568

389

MnO4 + 2H2O + 3e = MnO2 + 4OH

0,57

390

2AgO + H2O + 2e = Ag2O + 2OH

0,57

391

CH3OH (A) + 2H+ + 2e = CH4 + H2O

0,58

392

MnO24 + 2H2O + 2e = MnO2 + 4OH

393

PtBr42 + 2e = Pt + 4Br

0,535

0,58
0,58

174

STT

Phn ng in cc

Eo(V)

394

Sb2O5 + 6H+ + 4e = 2SbO+ + 3H2O

0,581

395

ClO2 + H2O + 2e = ClO + 2OH

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

2NO + 2H+ + 2e = H2N2O3

0,60

401

BrO3 + 3H2O + 6e = Br + 6OH

0,61

402

Hg2SO4 + 2e = 2Hg + SO24

0,615

403

ClO3 + 3H2O + 6e = Cl + 6OH

0,62

404

HNO2 + 5H+ + 4e = NH3OH + H2O

0,62

405

UO22+ + 4H + 2e = U

0,62

406

PtBr6 + 2e = PtBr4 + 2Br

0,63

407

2HgCl2 + 2e = Hg2Cl2 + 2Cl

0,63

408

PdCl24 + 2e = Pd + 4Cl

0,64

409

AgC2H3O2 + e = Ag + CH3COO

0,643

410

Au ( CNS )4 + 2e = Au ( CNS )2 + 2CNS

0,645

411

Ag2SO4 + 2e = 2Ag + SO24

0,653

412

Cu2+ + Br + e = CuBr

0,657

413

HN3 + 11H+ + 8e = 3NH4+

0,66

414

Au ( NCS )4 + 3e = Au + 4NCS

4+

+ 2H2O

0,66

175

Eo(V)

STT

Phn ng in cc

415

ClO2 + H2O + 2e = ClO + 2OH

0,66

416

AgBrO3 + e = Ag + BrO3

0,68

417

Sb2O4 + 4H+ + 2e = 2SbO+ + 2H2O

0,68

418

2H2SO3 + 4e + 2H+ = S2O32 + 3H2O

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

C6H4O2 + 2H+ + 2e = C6H6O2

0,699

423

H3 IO42 + 2e = IO

424

Te + 2H+ + 2e = H2Te

0,70

425

IrO2 + 4H+ + e = Ir3+ + 2H2O

0,70

426

PtCl62 + 2e = PtCl24 + 2Cl

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

H2SeO3 + 4H+ + 4e = Se + 3H2O

0,74

431

2NH2OH + 2e = N2H4 + 2OH

0,74

432

Ag2O3 + H2O + 2e = 2AgO + 2OH

0,74

433

H3SbO4 + 2H+ + 2e = H3SbO3 + H2O

0,75

434

NpO2+ + 4H + e = Np

0,75

435

BrO + H2O + 2e = Br + 2OH

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

RuO2 + 4H+ + 4e = Ru + 2H2O

0,79

440

Ag+ + e = Ag

0,7991

441

2NO3 + 4H + 2e = N2O4 + 2H2O

0,80

442

Pb(OH)4 + 2e = Pd(OH)2 + 2OH

0,80

443

Rh3+ + 3e = Rh

~ 0,8

444

AuBr4 + 2e = AuBr2 + 2Br

0,82

445

OsO4 + 8H+ + 8e = Os + 4H2O

0,85

446

2HNO3 + 4H+ + 4e = H2N2O2 + 2H2O

0,86

447

Cu2+ + I + e = CuI

0,86

448

HNO2 + 7H+ + 6e = NH4+ + 2H2O

0,86

449

AuBr4 + 3e = Au + 4Br

450

2IBr2 + 2e = I2 + 4Br

451

HO2 + H2O + 2e = 3OH

0,88

452

N2O4 + 2e = 2NO2

0,88

453

ClO + H2O + 2e = Cl + 2OH

0,89

454

CoO2 + H2O + 2e = CoO + 2OH

0,9

455

FeO24 + 2H2O + 3e = FeO2 + 4OH

0,9

456

2Hg2+ + 2e = Hg 22+

0,920

457

PuO22+ + e = PuO2+

0,73

458

NO3 + 3H + 2e = HNO2 + H2O

0,94

0,87

0,87

177

STT

Phn ng in cc

Eo(V)

459

NO3 + 4H + 3e = NO + 2H2O

0,96

460

AuCl4 + 2e = AuCl2 + 2Cl

461

AuBr2 + e = Au + 2Br

0,96

462

Pu4+ + e = Pu3+

0,97

463

Pt(OH)2 + 2H+ + 2e = Pt + 2H2O

0,98

464

Pd2+ + 2e = Pd

0,987

465

HIO3 + H+ + 2e = I + H2O

0,99

466

IrBr63 + e = IrBr64

0,99

467

ICl3 + 2e = ICl + 2Cl

0,99

468

HNO2 + H+ + e = NO + H2O

1,00

469

OsO4 + 6Cl + 8H+ + 4e = OsCl62 + 4H2O

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

H6TeO6 + 2H+ + 2e = TeO2 + 4H2O

1,02

474

2IBr + 2e = I2 + 2Br

1,02

475

N2O4 + 4H+ + 4e = 2NO + 2H2O

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

Se2Cl2 + 2e = 2Se + 2Cl

1,06

481

Br2 + 2e = 2Br

1,0652

482

N2O4 + 2H+ + 2e = 2HNO2

1,07

483

IO3 + 6H + 6e = I

484

HVO3 + 3H+ + e = VO2+ + 2H2O

485

Cu2+ + 2CN + e = CU (CN )2

486

AuCl2 + e = Au + 2Cl

487

PuO2+ + 4H + e = Pu

488

SeO24 + 4H + 2e = H2SeO3 + H2O

1,15

489

NpO22+ + e = NpO2+

1,15

490

ClO2 + e = ClO2

1,16

491

CCl4 + 4e = 4Cl + C

1,18

492

ClO4 + 2H + 2e = ClO3 + H2O

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

PdO3 + H2O + 2e = PdO2 + 2OH

1,2

498

ClO3 + 3H + 2e = HClO2 + H2O

1,21

499

O2 + 4H+ + 4e = 2H2O

1,229

500

IO3 + 6H + 2Cl + 4e = ICl2 + 3H2O

+ 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

MnO2 + 4H+ + 2e = Mn2+ + 2H2O

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

PdCl62 + 2e = PdCl24 + 2Cl

1,288

509

2HNO3 + 4H+ + 4e = N2O + 3H2O

1,29

510

Au3+ + 2e = Au+

~1,29

511

HBrO + H+ + 2e = Br + H2O

1,33

512

Cr2O72 + 14H + 6e = 2Cr

1,33

513

CrO4 + 8H + 7e =

Cr2 + 4H2O

1,34

514

NH3OH + 2H+ + 2e = NH4+ + H2O

1,35

515

Cl2 + 2e = 2Cl

1,3595

516

Tl3+ + Cl + 2e = TlCl

1,36

517

IO4 + 8H + 8e = I

518

RhO2+ + 2H+ + e = Rh3+ + H2O

1,4

519

2NH3OH+ + 2e = N2H4 + 2H2O

1,42

520

BrO3 + 6H + 6e = Br

521

Au(OH)3 + 3H+ + 3e = Au + 3H2O

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

PbO2 + 4H+ + 2e = Pb2+ + 2H2O

525

ClO3 + 6H + 5e =

526

HClO + H+ + 2e = Cl + H2O

1,49

527

Au3+ + 3e = Au

1,50

528

CeO2 + 4H+ + e = Ce3+ + 2H2O

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

HClO2 + 3H+ + 4e = Cl + 2H2O

534

HBrO + H+ + e =

535

2NO + 2H+ + 2e = N2O + 2H2O

1,59

536

Bi2O4 + 4H+ + 2e = 2BiO+ + 2H2O

1,59

537

H5IO6 + H+ + 2e = IO3 + 3H2O

1,6

538

Bk4+ + e = Bk3+

1,6

539

Ce4+ + e = Ce3+

1,61

540

2HClO + 2H+ + 2e = Cl2 + 2H2O

1,63

541

AmO22+ + e = AmO2+

1,64

542

HClO2 + 2H+ + 2e = HClO + H2O

1,64

543

NiO2 + 4H+ + 2e = Ni2+ + 2H2O

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

PbO2 + SO24 + 4H+ + 2e = PbSO4 + 2H2O

1,685

545

AmO22+ + 4H + 3e = Am

1,69

546

Pb4+ + 2e = Pb2+

1,69

547

MnO4 + 4H+ + 2e = MnO2 + 2H2O

1,695

548

AmO2+ + 4H + 2e = Am

1,725

549

H2O2 + 2H+ + 2e = 2H2O

1,77

550

Co3+ + e = Co2+

1,82

551

FeO24 + 8H + 3e = Fe

552

NH3 + 3H+ + 2e = NH4+ + H2

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

F2O + 2H+ + 4e = H2O + 2F

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

H2N2O2 + 2H+ + 2e = N2 + 2H2O

2,85

563

F2 + 2H+ + 2e = 2HF

3,06

3+

3+

3+

+ 2H2O

+ 2H2O

+ 4H2O

1,9

182

K hiu

p sut thm thu

, fN,fC

Hot trung bnh

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

Hot dung dch

S ti anion

Nng mol/l

Linh cation

Nng molan

Linh anion

Ha th

Th in cc

Hot s trung bnh

Sc in ng

H s chuyn in

S ti cation

183

Ti liu tham kho

1.

H.Kaesche. Korrozia metallov. Moscova Metallurgia, 1984.

2.

Mars G.Fontana. Corrosion engineering. Bortol, Massachusetts, 1986.

3.

Dieter Landolt. Corrosion et chemie de surfaces des mtaux. Press politech et

universitaies Romandes, 1994.

4.

UK Chatteryec- SK.Bose, SK Roy. Environmental degradation of metals. Newyork

Basel, 2001.

5.

Trnh Xun Sn. in ha hc. NXB HQGHN, ti bn 2004.

6.

WA.Schultze - Phan Lng Cm. n mn v bo v kim loi. Trng H Bch Khoa,

Trng H KT Delft - H Lan, 1985.

7.

Trng Ngc Lin. n mn v bo v kim loi. NXB KHKTHN, 2004.