ThS.

L NGOC TRUNG (CHU BIN)

G GI IA A O O 1 1R RI I^ ^H H

N
N
M
M
O
O

N
N
V
V
A
A

B
B
A
A

O
O
V
V

K
K
I
I
M
M
L
L
O
O
A
A

I
I












a Nng, thang 9 - 2005
(Luu hanh ni b)
LI GII THIU

n mon va bao v kim loai la mt nganh khoa hoc co lin quan n nhiu
lnh vc khac nhau: kim loai hoc, hoa l, hoa phn tch, hoa polimer, hoa mi
trng, hoa silicat .... Giao trnh c soan thao ngn gon, suc tch nhm giup cho
giao vin va sinh vin d oc va nm bt c vn mt cach d dang. Nhn
chung, cac chng c thit k t phn nh tnh, m ta bao gm nguyn l va cac
tnh cht nhit ng n phn nh lng bao gm cac phng phap ngn can va
cac phng phap kim tra. c bit, phn cui cung cp n mt s ng dung
mang tnh thc t cao. Tht vy, giao trnh nay co th cung cp thng tin cho ban
oc mt s kin thc mong mun.
Mt s kin thc v in hoa a c trnh bay kha chi tit trong cac
chng 2, chng 3 va chng 4, nhm giup cho sinh vin co mt cng cu
nghin cu v nhng vn phn tch va bao v kim loai khoi n mon. Chng 5
cp n vn thu ng hoa kim loai va cac phng phap in hoa chng n
mon. Chng 1 gii thiu tng quan v cac dang n mon thng gp trong thc t.
Hai chng cui cp n cac nhn t anh hng n tc n mon va mt s
phng phap co hiu qua c s dung chng n mon trong thc t.
Giao trnh nay khng phai la mt cm nang cho vn n mon va chng n
mon. iu cn nhn manh la cp n nguyn l va mt s phng phap a c
nghin cu lam giam tnh n mon cua kim loai trong thc th cng nghip hin
nay. Tht vy, muc ch cua giao trnh nay nhm gii thiu mt cach khai quat v
nguyn ly va cach phong chng n mon kim loai cho cac sinh vin khng thuc
chuyn nganh in hoa va n mon kim loai cac trng ai hoc va Cao ng ky
thut cac nm th hai va th ba hoc co th lam c s cho cac ngi bt u
nghin cu v nganh khoa hoc nay.
Tac gia xin chn thanh cam n B mn Cng ngh hoa hoc, Khoa Hoa ky
thut, lanh ao trng ai Hoc Bach Khoa a Nng cung nh ai Hoc a Nng
a tao moi iu kin thun li trong qua trnh bin soan va xut ban giao trnh nay.
Tuy vy, giao trnh nay con rt nhiu khim khuyt, rt mong c s gop
y cua cac c gia c bit la cua ng nghip, sinh vin va cac nha nghin cu
trong lnh vc n mon va chng n mon giao trnh ngay mt hoan thin hn.
Xin chn thanh cam n.
a Nng, ngay 20 thang 06 nm 2003
ThS. L NGOC TRUNG

CHUO^G 1
MO DU
I/ Tinh hinh n mon va bao v kim loai cua th gioi va Vit Nam.
II/ Dai cuong n mon:
1. Djnh ngha:
n mon kim loai la s t pha huy kim loai do tac dung hoa hoc va in hoa
gia chung vi mi trng bn ngoai.
Noi mt cach khac n mon la qua trnh chuyn bin kim loai t dang nguyn t
thanh dang hp cht. S n mon thng bt u xay ra trn b mt kim loai, ri
qua trnh phat trin vao su kem theo s bin i thanh phn va tnh cht hoa l cua
kim loai va hp kim. Kim loai co th hoa tan mt phn hay toan b tao ra cac san
phm n mon di dang kt tua trn b mt kim loai (lp g, oxyt, hydrat, ...)
2. Phn loai
2.1. Theo co cu cua qua trinh n mon
- n mon hoa hoc
- n mon in hoa
2.2. Theo diu kin cua qua trinh n mon
- n mon kh
- n mon kh quyn
- n mon trong cht in giai
- n mon trong t
- n mon do dong in ngoai
- n mon do tip xuc
- n mon do ng sut
- n mon do vi sinh vt
2.3. Theo dc trung cua dang n mon (Hinh 1.1)
- n mon u (thep cacbon trong dung dch axit sunphuaric)




- n mon khng u (thep cacbon trong nc bin)



- n mon chon la, tc ch mt pha b pha huy (gang trong axit)




- n mon vt, tao thanh nhng vt dai trn b mt (ng thau trong nc
bin)



- n mon h (n mon trong t)




- n mon im, ng knh t 0.1 2 mm (thep khng g trong nc bin)




- n mon di b mt




- n mon gia cac tinh th (thep crom 500
o
C 800
o
C)




- n mon nt, do tac ng ng thi gia n mon va c hoc (n mon canh
tuc bin)



Hnh 1.1

CHUO^G 2
N MON DIN HOA

I/ Khai nim
1.1. Gioi thiu:
Khi nghin cu s lam vic cua pin Cu-Zn trong dung dch in giai nao o
ta thy pha Zn mon dn do hin tng hoa tan. Nh vy Zn ong vai tro anod
trong pin Cu-Zn. Cac phan ng in cc xay ra nh sau:
Cu ) ( ) ( ) ( ) (
2 2
l Zn r Cu r Zn l
+ +
+ +
Zn ZnSO
4
CuSO
4
Cu (r)
Qua trinh anod Cu ni Qua trinh catod


Zn(r) Zn
2+
(l) Cu
2+
(l) Cu (r)

Trong thc t qua trnh n mon xay ra trn cung mt kim loai, ngha la trn
o ng thi xay ra qua trnh anod va catod, a n s pha huy kim loai.
K


A K A A
Hnh 2.1.
1.2. Phan ung din hoa:
Ky thut in hoa c s dung rng rai trong k thut va i sng. Tuy
nhin, trong n mon va trong nganh ma in vn cn quan tm o la c tnh
cua b mt phn pha gia kim loai-dung dch: v du, tc phan ng tai b mt,
tnh cht cua lp mang trn b mt hoc hnh dang cua b mt. Cng cu khao
sat va nghin cu cac tnh cht trn la th va dong. T hai thng s nay chung ta
co th suy lun moi th co th xay ra trn b mt phn pha. Khi chung ta nhung
mt thanh kim loai vao dung dch in li, th kim loai co khuynh hng phan ng
vi dung dch in li o: kim loai co th hoa tan tao thanh cation hoc cac
cation trong dung dch co th kt tua thanh kim loai:
V du: e Fe Fe 2
2
+
+
Hoc Fe e Fe +
+
2
2
Kt qua cua nhng phan ng nay la kim loai co khuynh hng tch tu in
tch m hoc dng. S tch tu nhng in tch nay se lam thay i in th cua
kim loai va in th se at n gia tr khi tc cua hai phan ng at cn bng.
in th nay goi la in th cn bng.
Mt iu quan trong, khi cho mt manh kim loa vao dung dch in li
in th cn bng cua no, iu nay khng co nghia la tc hoa tan kim loai va
phan ng kt tua kim loai la bng khng. Phan ng in hoa lun lun la mt qua
trnh chuyn in tch, chung ta co th nh ngha tc cua cac phan ng nay
bng mt dong. Khi tc phan ng hoa tan kim loai bng tc phan ng kt
tua kim loai th chung ta co th nh ngha tc cua cac phan ng nay bng mt
dong trao i.
Trong n mon kim loai co hai phan ng quan trong khac la phan ng kh
oxy hoa tan tao thanh ion hydroxyl va phan ng kh ion hydro hoc phn t
nc tao thanh kh hydro:

+ + OH e O H O 4 4 2
2 2

2
2 2 H e H +
+

+ + OH H e O H 2 2 2
2 2
S cn bng gia mt hoc nhiu phan ng catod vi phan ng anod hoa
tan kim loai th ta xac nh c mt dong n mon. Mt trong nhng ng dung
phng phap in hoa nghin cu n mon la xac nh ln cua mt dong
n mon va c ch cua qua trnh n mon.
1.3. Djnh lut Faraday:
Cac phan ng in hoa hoc san xut ra electron hoc tiu thu electron.
Dong electron c o bng dong I (A). Theo nh lut Faraday t l gia khi
lng cht phan ng m, vi dong I, c xac nh nh sau:

nF
Ita
m = (1)
F: hng s Faraday (=96500 coulomb)
n: s electron trao i
a: khi lng nguyn t
t: thi gian
Chia phng trnh (1) cho thi gian t va din tch b mt A, ta xac nh
c tc n mon r:

nF
ia
tA
m
= = r (2)
i: mt dong (
A
I
= i ).
Phng trnh (2) ch ra t l gia khi lng kim loai mt i trn mt n v
din tch trong mt n v thi gian (v du: mg/dm
2
/ngay) va mt dong I (v du:
mA/cm
2
).
II/ Din th din cuc:
2.1. Lop din tich kep:
Khi cho kim loai tip xuc vi cht in giai th xay ra s tac dung gia kim
loai vi cht in giai o. Trn gii han phn chia gia hai pha in cc-dung dch
se xut hin lp in tch kep (chiu day cua lp nay <0.1nm) va bc nhay th
c goi la in th in cc. Co nhiu l thuyt m ta cu truc cua lp in tch
kep nay nh l thuyt cua Helmholz, Gouy-Chapman va Gouy-Chapman-Stern.
2.2. Nguyn nhn xut hin lop din tich kep:
- Chuyn in tch t pha nay sang pha khac

+ -




e -
-
-
-
-
-
-
+ -
+ -
+ -
+ -
+ -
Hnh 2.2.
+
+
+
+
+
+
+
- Hp phu chon loc cac anion hay cac phn t lng cc trong dung dch









Hnh 2.3.
- Do hai nguyn nhn trn






Hnh 2.4.
-
-
-
-
-
-
-
+
+
+
+
+
+
+
2.3. Cac loai din cuc so sanh:
- in cc chun hydro (Standard Hydrogen Electrode: SHE)
Hay con c goi Normal Hydrogen Electrode: NHE
- in cc Calomel bao hoa (Saturated Calomel Electrode: SCE)
- in cc bac-clorua bac (Silver-Silver Chloride Electrode: Ag/AgCl)
III/ Phuong trinh dng hoc co ban cua qua trinh din cuc:
3.1. Nng luong hoat hoa tu do:
Xet mt in cc kim loai-ion kim loai ngha la in cc kim loai nhung
vao dung dch ch cha ion kim loai o. Trong trng hp nay cht kh (RED) la
nhng nguyn t kim loai trn b mt in cc, con cht oxy hoa (OX) la cac ion
kim loai trong dung dch:
Qua trnh oxy hoa: RED OX + ne (mt in t)
Qua trnh kh: OX + ne RED (nhn in t)
V du: Ag Ag
+
+ e
Kim loai Lop din tich kep Cht din li
G
(nng lng t do)

ion k.l. trong mang tinh th ion k.l. b hydrat hoa trong dung dch

*
G

*
G

Hnh 2.5
vi nFE G =
3.2. Qua trinh phn cuc hoat hoa o trang thai cn bng:
Nng lng hoat in hoa hoc i vi qua trnh chuyn in tch (k hiu
) cua mt phan ng in cc c xac nh bng tng cua:
_____
*
G
- Nng lng hoat hoa hoa hoc ( ) i vi phan ng catod:
*
c
G
OX + ne RED
hoc nng lng hoat hoa hoa hoc ( ) i vi phan ng anod:
*
a
G
RED OX + ne
- Hiu ng in trng trong lp kep, yu t nay se lam tng hay giam nng
lng hoat hoa vt qua hang rao th nng va no bng mt ai lng nFE.
: h s chuyn in tch, c a ra n gian vic tnh toan anh hng
cua in trng i vi hang rao th nng (t pha kim loai la , con v pha dung
dch la (1-). Thng thng nhng phng trnh c dung trong ng hoc n
mon th = 0.5).
Nh vy: = (1)
_____
*
a
G E nF G
a

*
va = (2)
_____
*
c
G E nF G
c
+ ) 1 (
*

Kim loai Lop din tich kep Cht din li
G
(nng lng t do)






_____
*
a
G
*
c
G
*
a
G E nF
_____
*
c
G
E nF ) (1

Hnh 2.6
Tc phan ng in cc hoan toan phu thuc vao tn s giao ng cua
cac ion co th vt qua hang rao th nng gia hai pha in cc-dung dch hoan
thanh phan ng chuyn in tich.
Da vao phng trnh Gibbs va nh lut Faraday ta co:
* i vi phan ng RED OX + ne (phan ng anod hay qua trnh oxy
hoa)
] exp[
______
*
RT
G
C nFf i
a
RED a a

= (3)
* i vi phan ng OX + ne RED (phan ng catod hay qua trnh kh)
] exp[ ) (
______
*
RT
G
C nFf i
c
OX c c

= (4)
Thay gia tr (1) va (2) vao (3) va (4) ta co:
]
) (
exp[
*
RT
E nF G
C nFf
a
RED a a

=

i (5)
}
] ) 1 ( [
exp{ )
*
RT
E nF G
C nFf i
c
OX c c
+
=

( (6)
hay ] exp[
'
RT
E nF
C nFf i
RED a a

=

(7)
}
) 1 (
exp{ )
'
RT
E nF
C nFf i
OX c c

=

( (8)
Vi ) exp(
*
'
RT
G
f f
a
a a

= va ) exp(
*
'
RT
G
f f
c
c c

=
trang thai cn bng ng: RED = OX + ne
Ta co:
0
) ( ) ( i i i
cb c cb a
= =
Nh vy, ta co:
}
) 1 (
exp{ ] exp[
' '
RT
E nF
C nFf
RT
E nF
C nFf
cb
OX c
cb
RED a

=

(9)

RED a
OX c cb
C f
C f
E
RT
nF
'
'
) = exp( (10)

RED
OX
a
c cb
C
C
f
f
E
RT
nF
ln ln
'
'
+ = (11)

RED
OX
a
c cb
C
C
nF
RT
f
f
nF
RT
E ln ln
'
'
+ = (12)
Phng trnh (12) co th vit di dang in th in cc, trong o E khac
vi E mt ai lng nao o:
RED
OX
a
c cb cb
C
C
nF
RT
f
f
nF
RT
E E ln ) ln (
'
'
+ + = + = (13)
C
OX
, C
RED
: nng cht oxy hoa va cht kh tai in cc trang thai cn bng.
iu kin chun: l mol C C
RED OX
/ 1 = =

0
E E
cb
= (in th in cc chun)

RED
OX cb
C
C
nF
RT
E E ln
0
+ = (14)
y chnh la phng trnh NERNST
3.3. Qua trinh phn cuc hoat hoa o trang thai khng cn bng:
Khi cn bng th tc anod bng tc catod. Khi cn bng in hoa b
pha v bng cach lam thay i nng lng t do cua cac cht phan ng n mt
gia tr khac, ngha la lam cho E E
cb
th luc o mt dong in anod hay catod
se c sinh ra do anh hng cua s di chuyn khoi gia tr E
cb
ti nng lng
hoat hoa cua phan ng catod hay anod. Trong trng hp nay ta co:
] exp[
' '
RT
E nF
C nFf i
RED a a

=

(15)
}
) 1 (
exp{ ) (
' '
RT
E nF
C nFf i
OX c c

=

(16)
' '
,
OX RED
C C : la nng cht kh va cht oxy hoa tai b mt in cc trang
thai khng cn bng
Phng trnh (15) va (16) co th vit lai nh sau:
]
) (
exp[
'
0
RT
E E nF
C
C
cb
RED
RED
a

i i = (17)
]
) ( ) 1 (
exp[ )
'
0
RT
E E nF
C
C
i i
cb
OX
OX
c

=

( (18)
Luc nay C : la nng cht kh va cht oxy hoa trong dung dch.
OX RED
C ,
Vi E - E
cb
= E - E
cb
= th luc nay mt dong in tng i
total
in
cc se la:
c a total
i i i + =
Hay ]}
) 1 (
exp[ ] exp[ {
' '
0
RT
nF
C
C
RT
nF
C
C
i i
OX
OX
RED
RED
total

= (19)
Phng trnh (19) la phng trnh c ban trong ng hoc cac qua trnh in
cc, no cho bit mi quan h gia tc phan ng i vi , C
RED
, C
OX
, i
o
, .
Nu nh qua trnh khuych tan nhanh th nng cac cu t phan ng tai
b mt in cc va trong th tch dung dch se nh nhau, co ngha la:
C va
RED RED
C =
'
OX OX
C C =
'
Nh vy phng trnh (19) se tr thanh:

]}
) 1 (
exp[ ] {exp[
0
RT
nF
RT
nF
i i
total

= (20)
Phng trnh nay c goi la phng trnh BUTLER-VOLMER. y la
phng trnh c ban cho tt ca cac qua trnh ng hoc cua phan ng in hoa.
IV/ Dng hoc cua cac qua trinh din cuc:
4.1. Phan ung din cuc bj khng ch boi giai doan chuyn din tich:
Nh a trnh bay, nu qua trnh khuych tan nhanh th nng cua cac cu
t phan ng xem nh bo qua. Luc o, tc cua qua trnh anod va catod nh sau
va c th hin bng 2 nhanh trn th i- (Hnh 2.7.)

RT
nF
i i
a

exp
0
= (21)
]
) 1 (
exp[
0
RT
nF
i i
c

= (22)


i=i
a
+ i
c
> 0

i
a



i
i
c



i=i
a
+ i
c
< 0
Hnh 2.7
* Qua th lon (trn th nu qua th dng ln th phan ng catod ring
phn co th bo qua va nu qua th m ln th phan ng anod ring phn co th bo
qua). Luc nay ta co:

a
a
a
RT
nF
i i

303 . 2
log log
0
+ = (>50mV) (22)

c
c
c
RT
nF
i i

303 . 2
) 1 (
log
0
log

= (> -50mV) (23)
Hay:
a
a a
i
nF
RT
i
nF
RT
log
303 . 2
log
303 . 2
0

+
a
= (24)

c
c c
c
i
nF
RT
i
nF
RT
log
) 1 (
303 . 2
log
) 1 (
303 . 2
0

= (25)
Dang tng quat:
i b a log + = (26)
Phng trnh (26) goi la phng trnh Tafel (Hnh 2.8). dc cua ng
thng ) (logi c goi la dc Tafel, c dung xac nh cac thng s ng
hoc cua qua trnh chuyn in tch i
o
, .
Vi
nF
RT
b
a
a

303 . 2
= va
nF
RT
c
c
) 1 (
303 . 2

= b


i
a


i
o




i
c


logi
Hnh 2.8
* Qua th nho, va gia su rng
a

c
0.5
Ta co:
RT
nF
i i
0
= (27)
Do o, ta co in tr phn cc R
p
:

0
nFi
RT
i
R
p
= =

(28)
Thay bng gia tr cua dc Tafel ta co:

p c a
c a
R b b
b b
i
) ( 303 . 2
0
+
= (29)
Phng trnh (29) c goi la phng trnh Stern-Geary.
Chu y: gia tr b
c
trn c ly gia tr dng cho tng quat hoa. Thc ra b
c

mang gia tr m, va do o phn b chia trong phng trnh Stern-Geary phai la
2.303(b
a
-b
c
)R
p

4.2. Phan ung din cuc bj khng ch boi khuych tan:
Tc phan ng in cc cung co th b khng ch bi s vn chuyn cua
cac cu t phan ng n va i khoi b mt in cc. S chuyn vn nay co th do:
- S in di (do gradient in th gy ra): co th loai tr.
- S khuych tan (do gradient nng gy ra)
- S i lu (do gradient tc gy ra)
Gia s xet mt phan ng in cc trn o xay ra qua trnh kh:
2H
+
+ 2e H
2

S dung m hnh NERNST (Hnh 2.9.):
Nng
C
0
2
H


0
)
= x
dx
dC
(


'
C
2
H


khoang cach x
Hnh 2.9.
: nng ion H
0
2
H
C
+
trong dung dch
: nng ion H
'
2
H
C
+
trn b mt in cc
: chiu day lp khuych tan
S dung m hnh Nernst, cac nh lut Fick, va nh lut Faraday ta co:
) 1 log(
303 . 2
L
c
c
i
i
nF
RT
=
4.3. Su phn cuc lin hop:
Tng qua trnh phn cc catod (k hiu
T,c
) la tng cua qua trnh phn cc
hoat hoa va phn cc nng :

conc c act c T
+ =
, ,

vi
0
0 ,
log log
) 1 (
303 . 2
log
) 1 (
303 . 2
i
i
b i
nF
RT
i
nF
RT
c
c c
c c
c act
=

) 1 log(
303 . 2
L
c
conc
i
i
nF
RT
=

) 1 log(
303 . 2
log
0
,
L
c c
c c T
i
i
nF
RT
i
i
b + =


Con i phan ng anod hoa tan kim loai th phn cc nng xem nh
khng ang k (co th bo qua). Do o:


0
log
i
i
b
a
a a
=

nhanh anod (chuyn in tch khng ch)



i
L


i

nhanh catod
(chuyn in tch khng ch)


nhanh catod
(khuych tan khng ch)
Hnh 2.10.


























CHUO^G 3
LY THUYT N MON HN HOP

I/ Co cu n mon din hoa:
Kim loai Cht din li
Vung anod




Vung catod



Hnh 3.1.
Me ne
ne D D.ne
Me
n+

A
-

K
+

Gm 3 qua trnh:
1. Qua trinh anod: ne Me Me
O mH
2
n+
.mH
2
O
2. Qua trinh chuyn din tu thua:
3. Qua trinh catod: D + ne [D.ne]

II/ Diu kin nhit dng cua su n mon:
iu kin h nhn co th trao i in t vi h cho khi:

cb
M
cb
R
E E >
: in th cn bng cua h nhn
cb
R
E
: in th cn bng cua h cho (kim loai)
cb
M
E
Ji du: cho thanh st nhung trong dung dch acid vi pH = 1,
, l mol C
Fe
/ 10
6
2

=
+
atm P
H
1
2
=
H cho: e Fe Fe 2
2
+
+

V E
C
nF
RT
E E
cb
Fe Fe
Fe Fe Fe
cb
Fe Fe
62 . 0 10 log 03 . 0 44 . 0
ln
6
/
0
/ /
2
2 2 2
= + =
+ =

+
+ + +

H nhn:
2
2 2 H e H +

+

V E
pH E
cb
H H
cb
H H
06 . 0
059 . 0
2
2
/
/
=
=
+
+
Vy , nn st b n mon va co kh hydro thoat ra.
cb
M
cb
R
E E >
III/ n mon voi su khu phn cuc hydro va oxy:
3.1. n mon voi su khu phn cuc hydro:
3.1.1. Diu kin nhit dng:
Nhng qua trnh n mon kim loai ma cht kh phn cc la ion H
+
va san
phm thoat ra catod la H
2
, th c goi la n mon kim loai vi s kh phn cc
hydro: O H H O H H e O H H
2 2 2 2
2
1
. + + +
+

iu kin c ban:
cb
M
cb
H
E E >
2
3.1.2. Qua trinh din cuc:
Gm 6 giai oan:
1/ Cac ion H+ b hydrat hoa tao thanh cac ion hydroxon va khuych tan n
b mt catod.
2/ Phong in cua ion hydroxon tao thanh ion hp thu:
O H H e O H H
hp 2 2
. + +
+
3/ Mt phn nguyn t hydro tao thanh hoa tan vao kim loai
4/ Kt hp cac nguyn t hp phu:
2
H H H
hp hp
= + hay kh hp phu in
hoa: O H H e O H H H
hp 2 2 2
. + + +
+
5/ Khuych tan cac phn t H
2
vao dung dch sau o khuych tan vao
khng kh.
6/ Cac phn t H
2
trn b mt catod tp hp lai thanh bot kh va thoat ra
khoi b mt kim loai:

2 2 2 2 2 2 2
.... nH H H H H H H = + + + + + +












Kim loai Khng khi


6 5

Dung djch

4

3
2
1

p
Hnh 3.2.
3.1.3. Dc dim cua su khu phn cuc hydro:
- n mon vi s kh phn cc hydro co kem theo s kh phn cc oxy.
- S kh phn cc hydro phu thuc nhiu vao pH.
- S kh phn cc hydro phu thuc voa b mt kim loai, cac tap cht.
- n mon vi s kh phn cc hydro co kem theo s don cua thep.
3.2. n mon voi su khu phn cuc oxy:
3.2.1. Diu kin nhit dng:
Nhng qua trnh n mon kim loai ma cht kh phn cc la oxy hoa tan
trong dung dch theo phan ng sau, goi la n mon kim loai vi s kh phn cc
oxy:

+ + OH e O H O 4 4 2
2 2
iu kin c ban:
cb
M
cb
O
E E >
2
3.1.2. Qua trinh din cuc:
Gm 6 giai oan:
1/ Oxy trong khng kh khuych tan vao dung dch qua b mt K-L
2/ Oxy hoa tan vao dung dch nh chuyn ng i lu t nhin hay cng
bc.
3/ Chuyn oxy qua lp Pran.
4/ Chuyn oxy qua lp khuych tan .
5/ Ion hoa oxy
* Trong mi trng trung tnh-kim:

+ + OH e O H O 4 4 2
2 2
* Trong mi trng acid:
O O H e H
2 2
2 4 4 + +
+
6/ Khuych tan ion OH
-
ra dung dch.

Kim loai Khng khi O
2

1


6
Dung djch
2

5

4 3


p
Hnh 3.3.
IV/ Ly thuyt din th hn hop:
n mon kim loai trong dung dch "nc" la kt qua cua 2 hay nhiu phan
ng in cc xay ra trn b mt kim loai, trong o co mt phan ng anod (oxy hoa
kim loai thanh ion cua no thanh dang oxyt hay hydroxyt), ng thi cung xay ra
mt hoc nhiu phan ng catod (kh cac cu t oxy hoa co mt trong dung dch).
Ly thuyt hn hp c cp trong phn nay i vi qua trnh n mon
kim loai trong mi trng acid, trung tnh hay kim yu. Cac v du sau se cho thy
tc n mon c quyt nh bi tc cua giai oan chm nht trong qua trnh
chuyn in tch hoc qua trnh khuych tan cua phan ng anod hay catod.
V du: Nhung mt thanh st sach vao dung dch acid (pH < 2)
Trong h nay co 5 phan ng in cc c xet n:
i
a,Fe

Fe Fe
2+
+ 2e (1)
i
c,Fe

i
c,H+

2H
+
+ 2e H
2
(2) (dd acid)
i
a,H+


i
c,H2O

2H
2
O + 2e H
2
+ 2OH
-
(2a) (dd trung tnh-kim)
i
a,H2O


i
c,O2

O
2
+ 4H
+
+ 4e 2H
2
O (3) (dd acid)
i
a,O2


i
c,O2

O
2
+ 2H
2
O + 4e 4OH
-
(3a) (dd trung tnh-kim)
i
a,O2


Theo quan im nhit ng hoc th phan ng (2) va (2a); (3) va (3a) la nh
nhau, chung co cung in th in cc cn bng.
Gia s rng dung dch a ui ht kh loai tr kha nng phan ng (3) va
(3a) xay ra. Ngoai ra phan ng (2a) co mt dong trao i thp. V vy, phan
ng kh nc kho co th xay ra. Nh vy, trong h st - acid trang thai n nh
ta co st b hoa tan va kh H
2
thoat ra:
O anod: i
a,Fe

Fe Fe
2+
+ 2e
i
c,Fe

O catod:
i
c,H+

2H
+
+ 2e H
2

i
a,H+


Hai phan ng nay xay ra ng thi trn cung mt b mt. Mi phan ng co
in th in cc va mt dong trao i ring (Hnh 3.4.).







E(V)
e H H 2 2
2
+
+
0.1 - i
+
H o,
0.0
cb
H H
E
2
/
+
2
2
2 H e H +
+



i Fe
Fe Fe / , 0
2+
e Fe 2
2
+
+

cb
E
/

Fe Fe
2+
- 0.5 -
Fe + Fe e
+
2
2

logi
Hnh 3.4.

Hai in th in cc va cung tn tai trn cung mt b mt
va ca hai phai phn cc n mt gia tr in th trung gian chung , goi la in
th n mon. c coi nh mt in th hn hp v no la in th in cc lin
kt cua hai in cc ring phn cua phan ng (1) va (2). Tai tc cua phan
ng anod (1) cn bng vi tc phan ng catod (2). Vy tc hoa tan anod i
xem nh tc n mon :
cb
H H
E
2
/
+
a c
i i
cb
Fe Fe
E
/
2+
corr
corr
E
corr
E
corr
E
a
corr
i i = = (Hnh 3.5.)












E(V)

+
i
H o,

cb
H H
E
2
/
+
2 +
+

2
2 H e H
i
corr M
E E =
corr
i
/

Fe Fe , 0
2+
e Fe Fe 2
2
+
+


cb
Fe Fe
E
/
2+

logi
Hnh 3.5
.
Vy )] ( exp[ ) (
, 0 ,
cb
Fe corr
Fe
Fe corr Fe a corr
E E
RT
nF
i i i = =


Va )] (
) 1 (
exp[ ) (
, 0 ,
cb
H
corr
H
H
corr
H c
corr
E E
RT
nF
i i i
+
+
+ +

= =


Phng trnh ng cong phn cc tng (Hnh 3.5.) cua phan ng n mon:

+
+ =
H c
Fe a total
i i i
,
,

Trong o:

)] ( exp[
)] ( exp[ )] ( exp[
)] ( ) ( exp[
,
, 0 ,
, 0 ,
corr
Fe
corr Fe a
cb
Fe corr
Fe
corr
Fe
Fe Fe a
cb
Fe corr corr
Fe
Fe Fe a
E E
RT
nF
i i
E E
RT
nF
E E
RT
nF
i
E E E E
RT
nF
i i
=
=
+ =

Tng t ta co: )] (
) 1 (
exp[
,
corr
H
corr
H c
E E
RT
nF
i i

=
+
+

: la gia tr phn cc cua in cc b n mon. K hiu .
corr
E E
Vy }]
) 1 (
exp{ [exp

RT
nF
RT
nF
i i
H Fe
corr total
+

=
` lon: tng t nh chng 2, ta co phng trnh Tafel dang tng quat
i a log + =
Vi
nF
RT
a
a

303 . 2
= va
nF
RT
c
c
) 1 (
303 . 2

=
` be: tng t nh chng 2, ta co:

RT
nF
i
corr
= i
hay
corr
i
i
nF
RT
=
Goi R
p
la in tr phn cc, ta co:

corr
p
nFi
RT
di
d
R = =
=0
) (

Thay bng gia tr cua dc Tafel ta co:

p c a
c a
corr
R
i
) ( 303 . 2

+
=

E(V)


cb
H H
E
2
/
+




Fe Fe
2
2 2 H e H +
+
corr
E
e 2
2
+
+



E
cb
Fe Fe /
2+
i
Hnh 3.6.











E(V)

+
i
H o,

cb
H H
E
2
/
+
2 +
+

2
2 H e H
i
corr
E
corr
i
/

Fe Fe , 0
2+
e Fe Fe 2
2
+
+


cb
Fe Fe
E
/
2+

logi
Hnh 3.7.
-1
-0.9
-0.8
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
0
-8 -7 -6 -5 -4 -3 -2 -1 0 1 2 3 4 5 6
x(i=10E+x)(mA/cm2)
E
(
v
o
l
t
)
H+->H2(M)
H+->H2(N)
sum(ic)
N->Nn+
M->Mm+
sum(ia)

Hnh 3.8.








CHUO^G 4
GIAN D DIN TH-pH (POURBAIX)

I/ Gioi thiu:
n mon kim loai trong dung dch "nc" la kt qua cua phan ng anod oxy
hoa kim loai cung vi mt hoc nhiu phan ng catod kh ion hydro hoc nc,
hoc oxy hoa tan. Vic xay ra cac phan ng ring phn nay phu thuc vao in th
cn bng cua anod va catod ring phn o: , , va .
cb
Me Me
n
E
/
+
cb
H H
E
2
/
+
cb
O H O
E
2 2
/
Theo phng trnh NERNST 25
o
C:
(1)
2
2
log 030 . 0 059 . 0
/
H
cb
H H
P pH E =
+
(2)
2 2 2 2 2
log 015 . 0 059 . 0
0
/ / O O H O
cb
O H O
P pH E E + =
Ca hai phng trnh trn u phu thuc vao pH va ap sut ring phn cua
kh tng ng.
Mt khac phan ng anod ring phn cung phu thuc vao pH:
Me + OH
-
Me(OH)
2
+ 2e
d dang khap sat mi quan h gia E-pH ta co th ve gian E-pH goi
la la gian POURBAIX.
Trn gian POURBAIX co 3 vung:
1/ Khi kim loai trang thai n nh v mt nhit ng, luc nay ta noi rng
kim loai se khng b n mon.
2/ Khi tao thanh cac san phm n mon co kh nng hoa tan, ta noi rng kim
loai trang thai hoat ng va tc n mon se tng manh.
3/ Khi tao thanh cac san phm n mon khng b hoa tan, ta noi rng kim
loai trang thai thu ng va tc n mon se xay ra chm.
II/ Gian d E-pH cua nuoc sach o 25
o
C:
Trong nc sach khi tip xuc vi khng kh, ngoai cac phn t H
2
O ra con
co mt lng rt nho ion H
+
va OH
-
, cung vi kh hoa tan ma quan trong la la kh
O
2
.
* i vi phan ng: 2H
+
+ 2e H
2

Phan ng trn cung co th vit lai di dang sau (trong mi trng trung tnh hay
kim)
2H
2
O + 2e H
2
+ 2OH
-
( E
H
0
) V
O H
83 . 0
/
2 2
=
theo phng trnh NERNST ta co: (ng a) at P
H
1
2
= pH E
cb
H H
059 . 0
2
/
=
+
* i vi phan ng: O
2
+ 4H
+
+ 4e 2H
2
O
( E
H
0
/
2
) V
O O
237 . 1
2
+ =
Phan ng trn cung co th vit lai di dang sau (trong mi trng trung tnh hay
kim)
O
2
+ 2H
2
O + 4e 4OH
-

( E
0
/

) V
OH O
411 . 0
2
+ =
theo phng trnh NERNST ta co: (ng b) at P
O
1
2
= pH E
cb
O
059 . 0 23 . 1
2
=
* i vi phan ng: H
+
+ OH
-
H
2
O
Vi hay 14 * =
+
OH H
C C 14 = + pH pOH
GIAN D E-pH CUA H2O
-2
-1.5
-1
-0.5
0
0.5
1
1.5
2
-2 0 2 4 6 8 10 12 14
pH
E
(
V
)
a
b
O
2

H
2

2H
+
+ 2e=H
2

O
2
+4H
+
+4e =2H
2
O
H
+
+ OH
-
=H
2
O
Hnh 4.1.
ng a va b chia gian thanh 3 vung. Vung trn cung ( in th cao)
nc co th b oxy hoa tao thanh oxy, vung thp nht ( in th thp) nc co th
b kh thanh hydro. Con vung gia (vung trung gian) ng vi trang thai bn cua
nc.
III/ Gian d E-pH cua h Fe-H
2
O o 25
o
C:
Ngoai cac cu t k n: H
2
O, H
+
, OH
-
, O
2
va H
2
, con phai k n cac
cu t khac nh: Fe, Fe
2+
, Fe
3+
, HFeO
2
-
, Fe(OH)
2
, Fe(OH)
3
.
Bang 4.1. ch ra nhng phan ng quan trong nht va cac phng trnh cn
bng iu kin:
V E V E
C C C C
l mol C C C
Fe Fe Fe Fe
OH Fe OH Fe
HFeO Fe Fe
77 . 0 ; 44 . 0
10 7 ) ( ; 10 9 . 1 ) (
; / 10
0
/
0
/
38 3 15 2
6
2 3 2
3 2
2
3 2
+ = =
= =
= = =
+ + +
+ +
+ +

Bang 4.1.
Phan ung Phuong trinh duong
e H H 2 2
2
+
+
pH E 059 . 0 =
a
e H O O H 4 4 2
2 2
+ +
+
pH E 059 . 0 23 . 1 + =
b
e Fe Fe 2
2
+
+

62 . 0 ) log( 0295 . 0 44 . 0
2
= + =
+
Fe E
1
e Fe Fe +
+ + 3 2
77 . 0 + = E 2
+ +
+ + H OH Fe O H Fe 2 ) ( 2
2 2
2
65 . 9 ) log( 5 . 0 65 . 6
2
= =
+
Fe pH
3
+ +
+ + H OH Fe O H Fe 3 ) ( 3
3 2
3

61 . 3 ) log(
3
1
613 . 1
3
= + =
+
Fe pH
4
e H OH Fe O H Fe 2 2 ) ( 2
2 2
+ + +
+
pH E 059 . 0 05 . 0 =
5
e OH Fe OH OH Fe + +

3 2
) ( ) ( pH E 059 . 0 27 . 0 + =
6
e H OH Fe O H Fe + + +
+ +
3 ) ( 3
3 2
2
pH E 177 . 0 41 . 1 + =
7
e H HFeO O H Fe 3 3 2
2 2
+ + +
+
pH E 0886 . 0 316 . 0 + =
8
+
+ H HFeO OH Fe
2 2
) ( 3 . 12 ) log( 3 . 18
2
= + =

HFeO pH
9
e OH Fe HFeO 2 ) (
3 2
+

46 . 0 ) log( 059 . 0 81 . 0
2
= =

HFeO E
10

ng 1 c tnh bng:
V Fe E E
Fe Fe
cb
Fe Fe
62 . 0 3 059 . 0 44 . 0 ) log(
2
059 . 0
2 0
/ /
2 2
= = + =
+
+ +

ng 5 c tnh nh sau:
T phan ng: (1) e Fe Fe 2
2
+
+
Ta co phng trnh: ) log(
2
059 . 0
2 0
/ /
2 2
+
+ =
+ +
Fe E E
Fe Fe
cb
Fe Fe

Vi phan ng: (2)
+ +
+ + H OH Fe O H Fe 2 ) ( 2
2 2
2
Ta co: T
2 2
) (
) )( (
2
+
= OH Fe
OH Fe
Cng phan ng (1) va (2) ta co phng trnh ng 5:
e H OH Fe O H Fe 2 2 ) ( 2
2 2
+ + +
+
Vi: ) log( 059 . 0
0
/ ) ( / ) (
2 2
+
+ = H E E
Fe OH Fe
cb
Fe OH Fe
V:
cb
Fe Fe
cb
Fe OH Fe
E E
/
/ ) (
2
2
+
=
Do o: )
) (
log(
2
059 . 0
2
/ ) (
0
/ /
2
2 2

+ =
+ +
OH
T
E E
Fe OH Fe
Fe Fe
cb
Fe Fe


2
/ ) (
0
/ /
) log( 059 . 0 ) log(
2
059 . 0
2
2 2

+ =
+ +
OH T E E
Fe OH Fe
Fe Fe
cb
Fe Fe

hay ) log( 059 . 0 14 059 . 0 ) log(
2
059 . 0
/ ) (
0
/ / 2
2 2
+
+ + + =
+ +
H T E E
Fe OH Fe
Fe Fe
cb
Fe Fe

Vy: 14 059 . 0 ) log(
2
059 . 0
/ ) (
0
/
0
/ ) (
2
2
2
+ + =
+
Fe OH Fe
Fe Fe
Fe OH Fe
T E E
Thay s vao ta co: 05 . 0
0
/ ) (
2
==
Fe OH Fe
E
Va phng trnh ng 5 nh sau: pH E 059 . 0 05 . 0 =
Gian d E-pH cua h Fe-H2O
2
HFeO2-
Fe
Fe2+
Fe3+
7
2
5
8
1
4
a
3
Fe(OH)3
Fe(OH)2
10
6
b
9
-1.5
-1
-0.5
0
0.5
1
1.5
2
2 4 6 8 10 12 14
pH
E
(
V
)

IV/ Cng dung cua gian d E-pH:
1/ Gian E-pH cua h kim loai-nuoc co 3 vung c trng:
a/ Vung kim loai cn bng vi ion kim loai nng 10
-6
mol/l.
Theo quan im n mon vung nay c goi la vung an toan.
b/ Vung hydroxyt kim loai (hay oxyt kim loai) cn bng vi ion kim
loai co nng 10
-6
mol/l. Vung nay thng kt tua day c va c goi la vung
thu dng.
c/ Vung kim loai hay hydroxyt kim loai (oxyt kim loai) cn bng vi
ion kim loai co nng 10
-6
mol/l. Vung nay xay ra cac phan ng n mon va
c goi la vung n mon.
2/ Trong mt gii han nao o, gian POURBAIX c a ra d oan
n mon. Tuy nhin, trn gian POURBAIX khng cho bit g v tc n mon
va ban cht bao v cua lp hydroxyt hay oxyt tao thanh trong vung thu ng.
3/ V nguyn tc co 3 phng phap chng n mon c rut ra t gian
POURBAIX:
a/ in th in cc co th lam m hn so vi in th n mon va
in th o kim loai nm trong vung an toan. Phng phap nay goi la bao v catod
(phn cc catod).
b/ in th in cc co th lam dng hn so vi in th n mon va
in th o kim loai nm trong vung thu ng. Phng phap nay goi la bao v
anod (phn cc anod).
c/ Co th chuyn pH sang phai cho kim loai ri vao vung thu
ng. Ngha la thay i mi trng co th dn n ngng n mon.

























CHUO^G 5
THU DNG HOA VA PHUONG PHAP BAO V DIN HOA

I/ Thu dng hoa kim loai:
1.1. Khai nim:
- Trang thai thu ng cua kim loai hay hp kim la trang thai ma trn b mt
cua no hnh thanh mt lp mang mong co tnh cht bao v kim loai hay hp kim
trong dung dch n mon. Lp mang nay co th day vai A
o
n vai trm A
o
va c
hnh thanh do qua trnh oxy hoa.
V du: e H OH Fe O H Fe 2 2 ) ( 2
2 2
+ + +
+
- c trng cho trang thai thu ng la khi kim loai b thu ng th in th
in cc cua no chuyn v pha dng hn (phn cc anod ln) va in tr n mon
ln, nn tc n mon giam nhanh.
- Hin tng thu ng do Lomonoxov tm ra nm 1738 va sau o c
Faraday phat trin thm vao nm 1840, khi ng nghin cu s n mon Fe trong
dung dch HNO
3
.
Tc n mon (g/m
2
.h)

1000 -



500 -



10 20 30 40 50 HNO
3
(%)
Hnh 5.1.
- Co hai cach chuyn kim loai vao trang thai thu ng:
* Phn cc anod (bng dong ngoai)
* Nhung vao dung dich in li co cha cu t thch hp.
1.2. Dng hoc cua qua trinh thu dng kim loai:
Gia s rng co mt s kim loai trong dung dch in li mt in th u
dng se xay ra phan ng sau:
(1) ye yH O Me O yH xMe
y x
2 2
2
+ + +
+
a/ Phn cuc anod:
V du: Fe b phn cc anod trong dung dch 0.5M H
2
SO
4
, bt u phn cc
t in th n mon E
corr
. (Hnh 5.2.)
E(V)
2 e H O O H 4 4
2 2
+ +
+
1.25 -

1.00 -
2 2
/ 10 7 m A i
pass

=


2 e H O Fe O H Fe 6 6 3
3 2 2
+ + +
+
+0.5 -


2 i =
2 3
/ 10 m A
cit

0.0 - FeSO
cb
H
E
2
2
2 2 H e H +
+
4

-0.25 -

-0.5 -
cb
Fe
E e Fe Fe 2
2
+
+
! ! ! !
-2 0 2 4 logi
Hnh 5.2.
b/ Nhung kim loai vao cht din li co cht oxy hoa thich hop:
Mun thu ng mt kim loai Me nao o th em nhung no vao trong dung
dch in li co cha cac cu t oxy hoa cua h oxy hoa kh (redox) co in th cn
bng dng hn . Trong trng hp ta co mt phan ng a in cc vi
in th hn hp ( ) c xac nh bng phan ng anod cua kim loai hoc oxyt
kim loai vi phan ng kh cua cht oxy hoa.
cb
redox
E
p
E
corr
E
Nu tc cua phan ng kh E ln hn tc phan ng anod ( i ) th
kim loai se b thu ng.
p crit
Cac iu kin thu ng kim loai bng h oxy hoa kh. H oxy hoa kh
thch hp cho s thu ng kim loai cn co nhng yu cu sau:
1/
cb
puqtd
E > (5a)
p
cb
redox
E E >
2/
crit redox c
i
p
>
,
E
i (5b)
Trong thc t cac h oxy hoa kh ap ng iu kin (5a), (5b) co th c
dung nh mt cht c ch thu ng trong dung dch n mon, chng han nh
Na
2
CrO
4
. Mt khac, nhng kim loai hoan toan b thu ng co th co hin tng n
mon cuc b. Hin tng nay la do s pha huy cuc b mang thu ng hoc bng
hoa hoc hoc bng c hoc. V du nh s pha huy mang thu ng bng cac yu t
hoa hoc do anh hng cua cac ion halogen c bit la Cl
-
, Br
-
, I
-
co mt trong mi
trng.
E(V)
Vung qua thu ng

cb
puqt
E

vung thu ng

cb
redox
E
corr
E
OX RED + ne

F
E
p
E vung chuyn tip

vung hoat ng
ne Me Me
n
+
+


logi
pass
logi
crit
logi
c,redox
logi
Hnh 5.3.
1.3. Bao v anod:
Trn c s phn tch s lam vic cua h thng n mon ta co th kt lun
rng nhiu trng hp kim loai b thu ng co th nng cao bn cua no bng
cach chuyn in th in cc v pha dng hn. Mun thc hin iu nay ta ni
kim loai cn bao v vi cc dng cua ngun mt chiu hay ni kim loai cn bao
v vi kim loai co in th in cc dng hn. Nhng hin nay vic ng dung
bao v anod vao thc t con nhiu han ch. Phng phap bao v anod chu yu
nng cao bn cua thep cacbon, thep khng g, hay titan trong mt s mi trng
nh xut c, axit sunphuaric co nng cao.
Dong bao v phai duy tr thng xuyn khi dong in chnh b ngt th phai
co dong phu.
Mun tin hanh bao v anod phai tun theo cac iu kin sau y:
- Trong mi trng o kim loai phai co kha nng thu ng khi phn cc
anod.
- Dong in be khi duy tr trang thai thu ng am bao bn n mon
cao, tiu hao nng lng t. Tuy nhin luc u phai cn mt dong ln vt
qua dong gioi han n vung thu ng cua kim loai.
- am bao co dong in thng xuyn khi bao v anod.
- vung in th hiu qua phai ln.
1uy nhin vic bao v anod thuong gp mt s kho khn nhu sau:
- Bao v anod khng thc hin c phn kim loai khng tip xuc vi
dung dch.
- Dong in ban u cho s thu ng anod ln nn cn phai co dung cu
khng ch in th va duy tr dong in.
- Rt kho khn bao v cho cac ng ng dn dai.
- Trong dung dch co cha cac ion hoat ng nh Cl
-
, th phai dung n ap
khng ch in th in cc cua kim loai vung thu ng nhng phai di in
th n mon l.
II/ Bao v din hoa bng cach thay di din th din cuc:
2.1. Khai nim:
Da trn th ng cong phn cc trong iu kin nao o ta co th
chuyn in th in cc v pha dng hn hay m hn so vi in th n mon th
dong in n mon co th giam. Nh vy, bao v in hoa la phn cc hoa in cc.
a/ Phn cuc anod:
Chuyn in th in cc v pha dng hn so vi in th n mon cho
n khi kim loai ri vao trang thai thu ng. Mun thc hin iu nay ta ni kim
loai cn bao v vi cc dng cua ngun mt chiu hay ni kim loai cn bao v
vi kim loai co in th in cc dng hn. Trong ca hai trng hp kim loai cn
bao v ong vai tro la anod. Cho nn tc n mon ch giam khi mi trng o
kim loai b thu ng.
b/ Phn cuc catod:
Chuyn in th in cc v pha m hn so vi in th n mon th hu
nh phan ng hoa tan kim loai ngng hn. Mun thc hin iu nay ta ni kim loai
cn bao v vi cc m cua ngun mt chiu hay ni kim loai cn bao v vi kim
loai co in th in cc m hn. Trong ca hai trng hp kim loai cn bao v u
ong vai tro catod, nn tc n mon se giam.
* Phn cc catod bng cach ni kim loai cn bao v vi cc m cua ngun mt
chiu, c goi la bao v catod din phn.
* Phn cc catod bng cach ni kim loai cn bao v vi kim loai khac co
in th in cc m hn, c goi la bao v bng Protector (anod hy sinh).
2.2. Bao v bng Protector:
Bao v bng Protector co th thc hin bng hai cach (Hinh 5.4.)

4




2

1


Gian tip Truc tip
1. Thit b cn bao v; 2. Protector Zn; 3. Cht boc Protector; 4. Dung cu kim tra
Hnh 5.4.
2.3. Bao v catod bng dong din ngoai:
Bao v catod bng dong ngoai co th lp t nh sau (Hinh 5.5.)

- +
4




5

Hnh 5.5.


3
V
1
A
3

3 2
1
1. Kim loai cn bao v 2. Anod phu 3. Cht boc
4. Ngun in mt chiu 5. in cc so sanh
Anod phu c ch tao t thep ph liu, re tin. Tuy nhin thng s dung
anod phu la in cc khng tan.
Mt s vt liu c dung lam anod phu nh sau (Bang 5.1.)
Bang 5.1.
Loai vt liu Dong cuc dai (A/m
2
) Dung luong (kg/A.nm)
Thep ph liu 5 10
Gang 35 0.1
Graphit 20 0.5
Ch (1%Ag; 6%Sb) 150 -
Ti
Ta + Pt
Nb

10.000

-

Tom lai, chon cach bao v bng protector hay bng dong ngoai phu thuc
chu yu vao cng trnh cn c bao v. i vi cng trnh nho phng phap dung
protector kinh t hn. Phng phap nay co u im la in th bao v phn b u.
Bao v catod bng dong ngoai c dung bao v nhng din tch ln,
nhng phng phap nay co th xay ra nguy c "qua bao v". Ngha la, in th
in cc cuc b cua cng trnh tr nn qua m n ni tc cua phan ng:

+ + OH H e O H 2 2 2
2 2
tr nn ang k.
Cac phng phap bao v trn thng c dung kt hp vi cac lp phu
cach in, nn vung tac dung bao v cua protector tng ln rt nhiu.




















CHUO^G 6
NHUNG NHN T ANH HUONG DN TC D N MON

I/ Nhung nhn t bn trong:
1.1. Tinh bn nhit dng cua kim loai:
in th in cc tiu chun co th anh ga gn ung tnh bn nhit ng
cua kim loai. Tc n mon cung co th tnh theo cng thc nh sau:

R
E E
I
cb
a
cb
c

=
I phu thuc vao va , tc phu thuc vao ban cht cua kim loai.
cb
c
E
cb
a
E
V du: - Trong mi trng trung tnh nhng kim loai nao co
in th in cc m hn se b hoa tan: Na, K, Zn, Al, Fe ...Nhng kim loai nao co
in th dng hn khng th hoa tan: Cu, Ag, Au, Hg, ...
V E
cb
H
41 . 0
2
=
- Trong mi trng axit nhng kim loai nao co in th in
cc m hn se b hoa tan: Zn, Al, Fe, Pb ...Nhng kim loai nao co in th dng
hn khng th hoa tan: Cu, Ag, Au, Hg, ... nhng khi trong dung dch co oxy hoa
tan th Cu, Hg, Ag lai b n mon do s kh phn cc oxy.
0
2

cb
H
E
2.2. Vj tri cua kim loai trong bang h thng tun hoan:
Khng phan anh ro net tnh bn chung cua kim loai v no con phu thuc vao
tnh cht bn trong va bn ngoai na. No ch phan anh mt s tnh cht co tnh qui
lut ma thi.
V du: - bn nhit ng cua kim loai tng t trn xung i vi cac
nhom IB, IIB, VIIIB.
- Nhng kim loai d b thu ng la nhng kim loai thuc nhom IVB,
VIB, VIIIB.
II/ Nhung nhn t bn ngoai:
2.1. Anh huong cua pH:
a/Anh huong truc tip: o la anh hng do cac phan ng kh phn
cc hydro va oxy. Khi thay i pH mt gia tr n v th in th se thay i
0.059V.
b/ Anh huong gian tip: thay i pH co th hoa tan san phm n
mon hay tao thanh mang bao v trn b mt in cc.
Ngi ta chia thanh 3 nhom (Hnh 6.1)


K K K







1 pH 2 pH 3 pH
Hnh 6.1.
* Nhng kim loai ma mang oxyt cua no hoa tan trong axit va trong kim:
Al, Zn, Sn, Pb. Trong mi trng axit no tao thanh cac ion kim loai Al
3+
, Zn
2+
,
Sn
2+
, Sn
4+
, ...Trong mi trng kim tao thanh phc cht ZnO
2
2-
, AlO
2
-
, ...(dang 1).
* Nhng kim loai ma mang oxyt cua no hoa tan trong axit ma khng b hoa
tan trong kim (do tao thanh cac oxyt kho tan): Ni, Co, Cu, Cr, Mn, Fe (dang 2).
* Nhng kim loai ma mang oxyt cua no khng hoa tan trong axit va trong
kim. Tc n mon khng phu thuc vao pH: Pt, Au, Ti, ... (dang 3).
i vi mi kim loai pH khac nhau co tc n mon khac nhau.
Bang 6.1.
Kim loai Al Pb Sn Zn Fe
pH co tc n mon cc tiu 6.6 8 8.5 11.5 14

2.2. Anh huong cua thanh phn va nng d cua dung djch mui:
Tc n mon in hoa phu thuc vao ban cht cua dung dch mui hoa
tan va nng cua no trong dung dch.
- Mui co tnh oxy hoa lam chm tc n mon, co khi ngn can hoan toan
qua trnh n mon do kim loai b thu ng: KClO
3
, K
2
CrO
4
, KNO
2
, ...Ngc lai nu
mui co tnh oxy hoa la cht kh phn cc th se lam tng tc n mon: S
2
O
8
2-
,...
- Nhng mui co tnh axit hay baz khi tng nng cua no th pH tng
nn co anh hng nh pH: Na
2
CO
3
, AlCl
3
, ...Tuy nhin, cung co nhng loai mui
axit khi tac dung vi kim loai tao thanh mui khng tan trn anod hay catod se lam
giam tc n mon: MeH
2
PO
4
, Me(HPO
4
)
2
, ...
- Tc n mon con phu thuc vao ban cht, nng cua cation va anion
cua mui hoa tan. Nu cac anion cua mui co kha nng hp phu trn b mt kim
loai lam thay i c cu lp in tch kep, lam giam in th in cc cua kim loai
lam cho tc n mon giam. Nhng nu anion co hoat tnh ln se pha v mang
thu ng nn tc n mon tng.
K(mm/nm) K(mm/nm)
KF

KCl KCl
NaCl
KBr
KI LiCl


t.gian nng
Hnh 6.2. Tc n mon phu thuc vao Hnh 6.3. Tc n mon phu thuc
Dang anion co trong dung dch vao dang cation va nng cua mui

2.3. Anh huong cua nng d oxy:
n mon kim loai trong a s cac trng hp do s kh phn cc cua oxy,
cho nn tc n mon phu thuc vao tc hoa tan cua oxy.
K






6 12 18 24 cm
3
/l
Hnh 6.4.
2.4. Anh huong cua nhit d:
Nhit anh hng ln n tc n mon. Trong dung dch in li tc
n mon tng khi tng nhit .






K





Hnh 6.5. T
2.5. Anh huong cua tc d chuyn dng dung djch:
Trong cng nghip hoa cht co rt nhiu thit b lam vic trong mi trng
cht in giai chuyn ng nh bm, van, ng ng, thap hp thu, hp phu, canh
khuy,... trong mi trng nay tc n mon co th tng hay giam.
- Nu cht long khng cha anion hoat ng: F
-
, Cl
-
, Br
-
, I
-
th ban u tng
tc chuyn ng cua cht long th tc n mon tng, nhng sau o giam. Nu
tng manh tc chuyn ng cua dong cht long th tc n mon tng.
- Nu trong cht in giai co cha cac anion hoat ng th khng th nao
tao mang thu ng. Do o, tc n mon tip tuc tng.
K K







m/s m/s
Hnh 6.6.
2.6. Anh huong cua dong din ro:
Rt nhiu thit b va ng ng lam vic ngm di at b n mon do tac
ng cua dong in ro (chu yu la dong mt chiu, dong xoay chiu khng anh
hng)







(+)



(-)



vung catod vung trung hoa vung anod (n mon manh)
Hnh 6.7.
2.7. Anh huong cua cac nhn t khac:
Do mt vai khu trong chi tit khng ung qui cach, gy nn n mon. Nguy
him nht la cac ch ni, ch han, cac mi han. (Hinh 6.8.)









Tranh bt mai mon D gy mai mon
Hnh 6.8.
III/ Cht lam chm n mon: (CLC)
3.1. Khai nim:
Cht lam chm n mon la cht khi thm vao mi trng mt lng nho th
tc n mon in hoa cua kim loai va hp kim giam i rt ln. C cu tac dung
cua cht lam chm la ngn can qua trnh anod va catod hay tao mang.
Theo Balezin cht lam chm co th chia lam cac loai sau:
Kiu A: Cht lam chm tao trn b mt hp kim mt lp mang mong.
Kiu B: Cht lam chm lam giam s xm thc cua mi trng.
Kiu AB: kt hp hai loai trn.
Ngoai ra theo mt s tac gia khac cht lam chm gm co cac loai sau:
Da vao thanh phn: CLC v c, CLC hu c.
Da vao tnh cht s dung: CLC trong dung dch, CLC bay hi.
Da vao tnh cht mi trng: CLC axit, CLC kim, CLC trung tnh.
danh gia CLC da vao hai ch s sau:
H s tac dung bao v (Z):
(%)
0
1 0
K
K K
Z

=
K
o
: Tc n mon kim loai trong dung dch cha co CLC (g/m
2
.h).
K
1
: Tc n mon kim loai trong dung dch khi co CLC (g/m
2
.h).
Hiu qua bao v ():
(%)
0
0
K
K
=
2.2. Cht lam chm anod:
Thng la nhng cht oxy hoa, nhng cht nay ngn can qua trnh anod, no
lam thu ng hoa b mt anod va lam giam qua trnh anod. Nhng CLC anod
thng c s dung: Na
2
CrO
4
, NaNO
2
, hn hp cua (NaNO
2
+ NaCO
3
), ...
V du: Cromat hoa b mt st, thep:

O O O O O O O O
Cr Cr Cr Cr Cr Cr Cr
O O O O O O O O

Fe Fe Fe Fe
Hnh 6.9.
3.3. Cht lam chm catod:
Thng la nhng cht hp thu oxy, do o lam giam tc n mon do s
kh phn cc oxy. Ngoai ra nhng cht nay lam giam hiu ng cua catod hay giam
b mt catod. Nhng CLC catod thng c s dung: Na
2
SO
3
, Ca(HCO
3
)
2
, NH
2
-
NH
2
, ZnSO
4
, ... Ngoai ra, cung co mt s ion kim loai nh As
3+
, Bi
3+
trong mi
trng axit chung se phong in trn catod tao thanh As hay Bi. Qua th hydro
trn cac kim loai nay cao hn qua th hydro trn thep.
3.4. Cht lam chm huu co:
Ngay nay, ngi ta a tm ra trn 3000 CLC, trong o a s la CLC hu c.
Tac dung cua CLC hu c la hp phu ln b mt kim loai va lam giam tc n
mon.
Anh hng cht hp phu n tc n mon do hai nhn t chnh:
+ Mc bao phu b mt bi ion hay phn t cua CLC hu c.
+ Thay i in th khi b hp phu.
Mt s CLC hu c thng c s dung trong mi trng axit H
2
SO
4
22%
nh sau:
Bang 6.2.
Tn cht Cng thc Nng Z(%) (%)
Utrotropin (CH
2
)
6
N
4
11.2% 96.798 3147
Thioure' (NH
2
)
2
CS 0.0050.01% 96 2425
Pyridin C
5
H
5
N 1.52% 40 1.7
Kaliiodua KI 0.11% 65 98.5
Benzidin NH
2
C
5
H
6
9g/l 87.7 96.5


3.5. Cht lam chm bay hoi:
Cht lam chm bay hi dung bao v kim loai khi tip kim loai o tip
xuc vi khoi hoc hi, nn c goi la CLC bay hi. CLC bay hi co ap sut hi
bao hoa cao, hi cua no nhanh chong chim y th tch khng gian kn, sau o
c hp thu ln b mt kim loai va bao v kim loai trong mt thi gian dai.
Nhung dc trung quan trong cua CLC bay hoi la:
+ P
hbh
= 10
-2
10
-4
mmHg 2025
o
C.
+ Co tac dung bao v kim loai lam vic trong khng gian kn.
Tac dung cua CLC bay hoi:
Cht lam chm bay hi co th tac dung vi cac cht kh phn cc, lam
giam m cua mi trng, lam cho b mt kim loai ghet nc, hay co th tao
mang thu ng.
Phuong phap su dung CLC bay hoi:
+ Cho CLC bay hi trong khng gian kn: phong, hom kn.
+ Quet CLC bay hi trn giy bao goi.
Mt s CLC bay hoi thuong duoc su dung:
+ CLC phtphat, loai nay thng c dung bao v thep, gang, crom,
niken, thic. Phi liu nh sau:
77% NaNO
2
+ 5.5% (NH
4
)
2
HPO
4
+ 1% Na
2
CO
3
(trong lng)
Hn hp nay dang bt, cho vao bao b va c 1m
3
khng gian cn 1.5kg
bt.
+ CLC bay hi trn c s natrinitrit va benzoat.
32.5% Benzoat + 16.5% NaNO
2
+ 1% (NH
4
)
2
CO
3
(trong lng)
3.6. Cht lam chm hoa tan trong du mo:
Cht lam chm hoa tan trong du m la hp cht hu c ma phn t cua no
co cu tao t hai phn:
+ Gc hydrocacbon co phn t cao (thng hay vong)
+ Nhom hoat ng bao v kim loai
Cng thc chung: C
n
H
2n+1
A.
A: -OH, -COOH, -COOMe, -SO
3
, --SO
3
Me, -NO
2
, -NH
2
.
Co cu tac dung cua CLC trong du mo:
+ Ngn can s khuych tan cua nc va kh n mon qua du m.
+ Tao trn b mt in cc mang hp thu ghet nc, khng cho nc i qua,
khng b nc phn huy.
Mt s cht CLC trong du mo hin nay duoc su dung:
Nitro hoa m khoang (co gn gc -NO
2
), hp cht hydrocacbon mach cao
co gn cac gc -SO
3
, -NO
2
, -NH
2
, hoc hn hp mt s m co nhiu gc hoat ng
th hiu qua bao v cao hn so vi n cht.

























CHUO^G 7
LOP PHU BAO V

Lp phu bao v la mt trong nhng phng phap ph bin nht hin nay chng
n mon kim loai.
Co ba loai lp phu bao v:
Lp phu kim loai
Lp phu phi kim loai
Lp phu bng cac hp cht hoa hoc.
A. Lop phu kim loai:
I. Co cu:
1.1. Lop phu anod:
in th kim loai phu m hn kim loai chnh, do o kim loai phu ong vai tro
anod cua pin n mon. V du : Zn, Sn, Cd, ... ln trn nn st, thep.
1.2. Lop phu catod:
in th kim loai phu dng hn kim loai chnh, do o kim loai phu ong vai tro
catod va kim loai chnh ong vai tro la anod. Do o, mun bao v kim loai chnh
lp phu phai am bao cac yu cu:
- Bn trong mi trng n mon.
- St chc, khng co l xp, khng co vt nt.
- Bam chc vao kim loai chnh.
V du: Cu, Cr, Ni ln trn nn st, thep.
II. Phuong phap phu:
2.1. Phuong phap din: s dung ngun in mt chiu
Ban cht cua phng phap nay la kt tua in hoa t cac kim loai khac.

+ -
R
A
Zn Fe








Hnh 7.1.
2.2. Phuong phap nhit:
Ban cht cua phng phap nay la nhung kim loai cn bao v vao kim loai khac
dang nong chay va kim loai nong chay bam ln b mt kim loai cn bao v.
Nhng yu cu c ban tao thanh lp phu:
- Kim loai nong chay co kha nng thm t va dang u trn b mt kim loai cn
bao v.
- Tao thanh hp kim gia hai kim loai.
- Nhit nong chay thp hn kim loai cn bao v.
* Uu dim: n gian, nng sut cao.
* ^huoc dim:
+ Chiu day lp phu khng n nh, phu thuc vao nhit va thi gian nhung.
+ Tiu hao kim loai kha ln (lam vic nhit cao nn kim loai d b oxy hoa)
+ Lp phu khng u, khng bng phng
+ Khng th thc hin c vi cac chi tit phc tap (l, khe)
2.1.1. Nhung kem:
Zn co in th m hn Fe nn co th bao v st khoi n mon trong khng kh va
trong nc.
a. Cac buoc tin hanh:
- Ty du m trong dung dch 6-10% NaOH, 2-5% Na
3
PO
4
80
o
C.
- Ty g hoa hoc trong dung dch 5-10% H
2
SO
4
thi gian 30-35' (co the ty g in
hoa)
- Hoat ng hoa b mt Fe trong dung dch 0.5-3% HCl hay trong dung dch
NH
4
Cl a acid hoa.
- Tr dung hoa b mt kim loai.
- Sy nhit 120-200
o
C.
- Nhung vao dung dch Zn nong chay.
b. Vai tro cua cht tro dung:
Muc ch cua cng oan nay la lam sach cac cht bn trn b mt kim loai
tranh cho kim loai khoi b oxy hoa va lam cho kim loai thm t tt vi kim loai
nong chay.
Cht tr dung chia lam hai loai:
* 1ro dung uot: 42-43% NH
4
Cl + 13-14% ZnO + 42-43% ZnCl
2
.
Cht tr dung nong chay trn kim loai nong chay.
Cac phan ng co th xay ra nh sau:
- Khi cht tr dung tac dung vi Zn nong chay:
Zn + 2NH
4
Cl Zn(NH
3
)
2
Cl
2

Zn(NH
3
)
2
Cl
2
ZnNH
3
Cl
2
+ NH
3

- Oxyt st b kh theo phan ng:
FeO + NH
4
Cl FeOHCl + NH
3

FeOHCl + ZnNH
3
Cl
2
FeCl
2
+ ZnOHCl + NH
3

ZnOCl ong vai tro chnh trong vic thm t b mt Fe. Vi vy, ZnCl
2
co vai tro
quan trong trong cht tr dung v:
ZnCl
2
+ H
2
O [Zn(OH)
2
Cl
2
]H
2
- Ngoai ra co cac phan ng sau:
FeCl
2
+ Zn ZnCl
2
+ Fe
ZnO + 2NH
4
Cl ZnCl
2
+ 2NH
3
+ H
2
O
* 1ro dungkh: 50% ZnCl
2
c hoa tan trong thit b ring, trc khi nhung Zn,
cho kim loai Fe nhung vao ZnCl
2
, sau o sy kh, nhung vao Zn nong chay.
2.1.2. Cu tao cua lop Zn:
Nhung Fe vao Zn nong chay tao thanh lp phu Zn. Lp phu nay co nhiu lp, qua
nghin cu cu tao cua no co th chia lam 6 lp:
- Lop : la lp dung dich rn chua khoang 95% trong lng Fe.
- Lop : co dang Fe
5
Zn
21
hay Fe
3
Zn
10
cha khoang 18-20% trong lng Fe.
- Lop : co dang FeZn
7
cha 7-12% trong lng Fe.
- Lop : co dang FeZn13 cha 6% trong lng Fe.
- Lop : ham lng Zn kha nhiu, ham lng Fe ch con 0.003%.
- Lop : la lp trung gian gia lp va lp . Lp nay don lam giam bn cua
lp phu.
Lp +: chiu day cua lp Zn chim 50-60% chiu day cua lp phu.
2.1.3. Anh huong cua nhit d va tap cht:
* Anh huong cua nhit d: nhit cang cao lp phu cang mong, chiu day cua
lp cang nho, nn Zn b oxy hoa cang cao gy tn tht ln. Ngc lai, nhit
cang thp chiu day lp phu cang ln, nhng lp phu t bng phng va kho thao
tac.
Thng thng khng ch nhit khoang 435-470
o
C.
* Anh huong cua tap cht: Al la nguyn t kha quan trong, nu trong Zn
nong chay co khoang 0.2-0.4% Al th du phng phap tr dung t hay kh u
cho lp Zn bong. Nhng nu ham lng Al nhiu hn se lam thay i tnh cht c
hoc cua lp phu.
Tng ham lng Al th chiu day cua lp se giam, lam cho chiu day chung
giam. Khi ham lng Al at n mt gii han nao o th lp trung gian bin mt
va nu ham lng Al vt qua 0.4% th AlCl
3
c tao thanh va lam can tr phan
ng gia Fe va Zn. Ngoai ra, cac tap cht khac nh: Pb, Cd, Bi cung anh hng
n chiu day cua lp phu Zn.
2.1.4. Cu tao cua thung nhung Zn:




1 2

3 4



5
Hnh 7.2.
1. Lp Zn nong chay; 2. Cht tr dung nong chay; 3. Lp Pb nong chay
4. Vt trang; 5. Vo thung (bng thep co lot lp gach samt)
2.2. Nhung thic: (oc tai liu)
B. Lop phu phi kim loai:
Co hai loai ph bin hn ca la sn va trang men.
I. Trang men:
Dung bao phu cac thit b phan ng co vo boc gia nhit, thap hp thu, ng trao
i nhit (rut ga), ...
1.1. Co cu bao v cua lop men:
Lp men bam chc vao kim loai, hoan toan khng co l xp. Nc va khng kh
khng th thm qua c. bn cua kim loai chnh la bn cua lp men. Kim
loai c trang men co nhng u, nhc im nh sau:
* Uu dim:
- Lp men tng i bn trong mi trng xm thc: kh quyn, dung dich mui
trung tnh, trong nc, trong acid co tnh oxy hoa, kim yu.
- Gi ve ep va n nh trong mt thi gian dai.
- Cng ngh trang men n gian, nguyn liu d tm.
* ^huoc dim:
- Khng the boc lp phu ra c, do o khi lp men h th khng th phuc hi chi
tit nh ban u c.
- Lp men d v do tac dung c hoc.
- Khng th thc hin c cho cac chi tit phc tap.
- trong mi trng kim manh, hoc mi trng HF lp men se b pha huy:
SiO
2
+ 2NaOH Na
2
SiO
3
+ H
2
O
SiO
2
+ HF SiF
4
+ 2H
2
O
1.2. Nguyn liu san xut men: co 2 nhom chnh
* Jt liu tao thanh thuy tinh: cat thach anh la vt liu chnh san xut ra men.
Thanh phn SiO
2
chim t 95-98.8%, nhit nong chay cao 1600-1700
o
C, cho
nn cn phai thm mt s cht phu gia.
* Cac cht phu gia: tuy thuc vao tnh cht cua men ma cho cac cht phu gia khac
nhau:
- Ha thp nhit nong chay dung Na
2
O.PbO
- Men bn hoa thm cac loai oxyt B
2
O
3
.PbO
- Anh hng h s gian n nhit thm Na
2
O.K
2
O
- Cht lam uc CaF
2
, 3NaF.AlF
3
(criolit Na
2
AlF
6
)
- Cht oxy hoa oxy hoa cacbon dang bn: NaNO
3
, KNO
3
, MnO
2
.
- Cht tao mau:
Pb
2
Pb
4
O
7
: mau vang
C
o
O + Cr
2
O
3
: mau xanh nc bin
Cr
2
O
3
: mau xanh la cy
1.3. Trang men:
* Men nn: phai am bao men bam chc vao kim loai, khng cho kim loai tac
dung vi mi trng xm thc. Chiu day cua lp men nay 0.1-0.2 mm.
* Men ngoai: trang tr va bn c hoc.
Trang men co th dung hai phng phap t hay kh.
II. Son:
Sn la loai cht long c cu tao t cht tao mang va mt s cht hoa tan trong
dung mi d bay hi. Tuy thuc vao cht tao mang ma co nhiu loai sn khac
nhau.
2.1. Vai tro cua lop son:
- Chng g
- Trang tr
- Cach in, sn chu nhit, chu ha, chu acid, chu kim, chu xng du.
2.2. Yu cu cua mang son:
- Sn phai bam chc vao kim loai nn.
- Phai n nh hoa hoc
- Khng thm nc, thm kh, khng b nc phn huy.
- Phai chm lao hoa.
2.3. Thanh phn mang son:
Cht tao mang: la thanh chu yu, cht tao mang co th la: du thao mc, nha
thin nhin, nha tng hp.
* Dung mi: cht long d bay hi, dung hoa tan cht tao mang.
* Bt mau: cac oxyt kim loai mn hoc cac bt mau hu c, khng hoa tan trong
nc, co tac dung lam cho mang sn nhn, co mau ep, co bn c hoc cao.
Lng bt mau chim khoang 10% trong lng sn.
2.4. qua trinh gia cng mang son:
- X l b mt trc khi sn
- Chon sn
- Cac lp sn
+ Sn nn: lam cho b mt khng g va lam nn
+ Sn lot: lam phng b mt lp sn nn
+ Sn phu: tuy theo yu cu va tac dung ma chon sn.
- Sy kh mang sn.
C. Lop phu hop cht hoa hoc:
I. Oxy hoa va nhum mau kim loai:
1.1. Oxy hoa kim loai den:
bao v kim loai en khoi n mon thng ngi ta tao trn b mt kim
loai o mt lp oxyt theo phng phap hoa hoc hay in hoa. Phng phap in
hoa t c s dung va khng c cp trong phn nay.
a. Oxy hoa theo phuong phap hoa hoc:
Qua trnh nay thng c tin hanh trong dung dch kim c co cha cac cht
oxy hoa.
Phng phap hoa hoc c dung ph bin hn phng phap in hoa.
C cu tao mang oxyt nh sau:
- Hoa tan Fe trong kim tao thanh mang oxyt (mui oxyt thp):
Fe Na
2
FeO
2

- Oxy hoa mui oxyt thp thanh mui oxyt cao:
Na
2
FeO
2
Na
2
Fe
2
O
4

- Tac dung hai mui trn tao oxyt st t:
Na
2
FeO
2
+ Na
2
Fe
2
O
4
Fe
3
O
4

- Thuy phn mui oxyt cao:
Na
2
Fe
2
O
4
+ (m+1)H
2
O Fe
2
O
3
.mH
2
O
- Kh hydrat hoa mt phn:
Fe
2
O
3
.mH
2
O Fe
2
O
3
.(m -1)H
2
O
Cac giai oan trn co th c tng quat nh sau:
Fe Na
2
FeO
2
Na
2
Fe
2
O
4
Fe
2
O
3
.mH
2
O Fe
2
O
3
.(m -1)H
2
O

Fe
3
O
4

(mang oxyt) (bun mau o kt tua trn ay thung)
Cu tao mang va chiu day mang phu thuc vao tc tao thanh trung tm
kt tinh va tc phat trin mang. Nu tc tao trung tm kt tinh ln hn tc
phat trin mang (nng cht oxy hoa cao) th mang tao thanh nhanh, st chc,
nhng mong. Ngc lai, Nu tc tao trung tm kt tinh be hn tc phat trin
mang (nng kim cao) th mang tao thanh day nhng xp.
Cht oxy hoa c s dung y la cac mui nitric va nitrat. Dung mui
nitric cho mau xanh sang, con mui nitrat cho mau en.

Bang 7.1. Thanh phn va ch oxy hoa
STT Thanh phn Ch oxy hoa

1
NaOH
NaNO
3

NaNO
2

700-800 g/l
200-250 g/l
50-70 g/l
138-140
o
C
(khi nhung)
142-146
o
C
(khi ly ra)

20-120 phut


2
NaOH
NaNO
3

1000-1100 g/l
130-140 g/l

145-150
o
C
(khi nhung)
160-165
o
C
(khi ly ra)

60-90 phut


Dung dch 1 cho mang oxyt bong, dung dch 2 cho mang oxut m.
Ngoai ra co th tin hanh oxy hoa kim loai en trong dung dch acid H
3
PO
4
th cho
mang oxyt tt hn v ca tnh cht c hoc va bn lin kt, bn n mon so vi
dung dch kim. c bit, qua trnh nay co th tin hanh oxy hoa cho ca kim loai
en va kim loai mau. Qua trnh tin hanh nhanh, t tn nhit lng.
Bang 7.2. Thanh phn va ch oxy hoa
Cu tu
Thanh phn (g/l) Nhit Thi gian
H
3
PO
4

Ca(NO
3
)
2
.4H
2
O
Ba(NO
3
)
2

MnO
2

Ni
Fe(H
2
PO
4
)
2

Mn(H
2
PO
4
)
2

4-10
70-100
-
1.0-2.0
-
-
4-10
-
70-100
1.0-2.0
8-10
-
2-10
-
70-100
1.0-2.0
-
30-40



100
o
C


40-45 phut

1.2. Oxy hoa kim loai mau:
bao v va trang tr kim loai mau, ngi ta thng tao trn b mt kim loai o
mt lp oxyt theo phng phap hoa hoc hay in hoa.
1.2.1. Oxy hoa dng:
Oxy hoa ng chng n mon, trang tr trong cng nghip va thit b quang hoc.
a. Oxy hoa theo phuong phap hoa hoc:
Mang oxyt tao thanh day khoang 1m, co thanh phn chu yu la CuO.
Thanh phn va ch oxy hoa nh sau:
NaOH 50 g/l
K
2
S
2
O
8
15 g/l
Nhit 60-65
o
C
Thi gian 5 phut
b. Oxy hoa theo phuong phap din hoa:
Mang oxyt tao thanh day khoang 1-2m, co bn c hoc va bn n mon cao
va co th oxy hoa cac loai hp kim cua Cu.
Thanh phn va ch oxy hoa nh sau:
NaOH 100-250 g/l
Nhit 80-90
o
C (Cu)
60-70
o
C (ng thau)
i
a
0.5 A/dm
2

in th 2-6 Volt
Thi gian 30 phut
oxy hoa va nhum mau vang cua ng, ngi ta khng s dung dong
in ngoai ma ch cho Cu tip xuc vi Al. Gia Cu va Al se xut hin mt hiu
in th.
Thanh phn va ch oxy hoa:
CuSO
4
50 g/l
NaOH 35 g/l
C
2
H
2
O
4
30 g/l
pH 9.2-9.6
Nhit 20-32
o
C
Thi gian 7 phut
T l b mt Cu:Al = 4:1
Dung dch khac nhau cho mau khac nhau va thi gian khac nhau cung cho
mau khac nhau.
1.2.2. Oxy hoa nhm:
a. Oxy hoa theo phuong phap hoa hoc:
Oxy hoa Al theo phng phap nay, chiu day mang oxyt Al at c khng
cao khoang 0.5 - 1m va co bn kem.
Thanh phn va ch oxy hoa:
Na
2
CO
3
50 g/l
NaOH 2-2.5 g/l
Na
2
CrO
4
15 g/l
Nhit 80-100
o
C
Thi gian 5-30 phut
b. Oxy hoa theo phuong phap din hoa:
- Co cu tao mang oxyt:
Qua trinh anod:
Al Al
3+
+ 3e (1)
OH
-
O
2
+ H
2
O + 4e (2)
Qua trnh nay co th chia lam nhiu giai oan:
2OH
-
O
2-
+ H
2
O
O
2-
O
-
+ e
O
-
O + e
2O O
2
2Al
3+
+ 3O
2-
Al
2
O
3
(3)
2Al + 3O Al
2
O
3
(4)
Qua trinh catt:
H
+
+ 2e H
2
(5)
Nhm khi mi cho vao dung dch in li co th xay ra phan ng sau:
2Al + 3H
2
SO
4
Al
2
(SO
4
)
3
+ 3H
2
(6)

Mang c hnh thanh se tac dung vi dung dch in li:
Al
2
O
3
+ 3H
2
SO
4
Al
2
(SO
4
)
3
+ 3H
2
O (7)
- Co cu phat trin mang oxyt va hinh thanh cac l xp:
Qua trnh tao mang oxyt xay ra theo phan ng (3) va (4). Lp oxyt nhm
mi hnh thanh mong st va chiu day hu nh khng thay i. Khi a tao mang
oxyt th cung tn tai hai qua trnh la phat trin mang va hoa tan mang (phan ng
7). Qua trnh hoa tan nay lai trn b mt lp oxyt nhm nhiu l xp, luc nay
oxy nguyn t va ion oxy khuych tan qua mang di ay cac l xp o tip tuc
oxy hoa nhm. Lp oxyt mi lai c hnh thanh, lp nay nm gia b mt phn
chia kim loai va oxyt, phn nay se phat trin v moi hng la lam cho lp oxyt day
thm. Mt khac, trn day l xp pha ngoai mang se xay ra qua trnh hoa tan mang
oxyt. Hai qua trnh xay ra ng thi va canh tranh nhau. Nu tc phat trin
mang ln hn tc hoa tan mang th lp oxyt day se c tao thanh. Ngc lai,
tc phat trin mang nho hn hoc bng tc hoa tan mang th lp oxyt se
khng c tao thanh hoc b hoa tan.
Tom lai, lp oxyt bao gm hai lp: lp trong cung mong st, lp ngoai day
co nhiu l xp (chnh l xp la cac trung tm phat trin mang).
Ngoai ra, trn thanh cac l xp ngoai cung co ca phan ng hydrat:
Al
2
O
3
+ H
2
O Al
2
O
3
.H
2
O (8)
Hay Al
2
O
3
+ 3H
2
O Al
2
O
3
.3H
2
O (9)
Va cung co qua trnh hoa tan:
Al
2
O
3
.nH
2
O + 3H
2
SO
4
Al
2
(SO
4
)
3
+ (n+3)H
2
O (10)
Chu y:
- S phat trin mang oxyt phu thuc vao t l tc cua hai qua trnh din
bin ng thi: s hnh thanh mang nh oxy hoa in hoa va hoa tan mang do tac
dung cua cht in li.
- Tc tao mang c xac nh bng mt dong (i
a
cao tao mang
nhanh). Tc hoa tan mang phu thuc vao ban cht va nhit cua dung dch
in li (nhit cao, tc hoa tan mang ln).
- 1hanh phn va ch d oxy hoa:
Co th s dung nhiu loai cht in li khac nhau tuy thuc vao muc ch s
dung mang oxyt, nhng thng thng ngi ta hay s dung dung dch H
2
SO
4
lam
cht in li.
Dong in s dung co th la dong xoay chiu hay mt chiu, nhng dung
dong mt chiu cho mang oxyt cng, st hn.

Bang 7.3. Thanh phn va ch oxy hoa
Thanh phn va ch Dong mt chiu Dong xoay chiu
H
2
SO
4
(g/l)
Nhit (
o
C)
i
a
(A/dm
2
) Al
i
a
(A/dm
2
) Dura
in th (Volt) Al
in th (Volt) Dura
Thi gian (phut)
180-200
15-23
1.5-2
0.8-1.2
12-13
13-28
40-50
125-130
12-25
1.5-2
1.5-2
21-28
19-26
40-50 (Al)
30-40 (Dura)
Chu y: mun co mang oxyt day, chu mai mon phai oxy hoa trong dung dch lanh
13
o
C, i
a
=22.3 A/dm
2
, thi gian = 34 h.
1.2.3. Nhum mau nhm va hop kim nhm:
Do mang oxyt co nhiu l xp nn co kha nng hp phu cac cht mau hu
c, v c, di khi cac cht mau nay tac dung vi mang oxyt tao thanh cac hp cht
hoa hoc. Ngoai ra, cac phan ng tao mau co th xay ra trn l xp lam cho mang
oxyt co mau.
V du: mun nhum mau vang da cam cho nhm, ngi ta nhung mu
nhm a ant hoa vao dung dch 510g/l K
2
Cr
2
O
4
thi gian khoang 30 phut, ra
sach, sau o em nhung vao trong dung dch 50100g/l AgNO
3
cung trong thi
gian 30 phut. Mau cua mang oxyt se xut hin do phan ng sau
K
2
Cr
2
O
4
+ AgNO
3
= Ag
2
Cr
2
O
4
+ 2KNO
3

vang da cam
Bang 7.4. Thanh phn dung dch khi nhum mau cac hp cht v c.
Dung dch 1 Dung dch 2 Mau
nhum
Mui
Nng
(g/l)
Mui Nng
(g/l)
Hp cht
mau
Xanh FeCl
2
10-100 K
4
Fe(CN)
6
10-50 Xanh da tri
Da lng CuSO
4
10-100 K
4
Fe(CN)
6
10-50 CuFe(CN)
6

Vang Pb(CH
3
COO)
2
100-200 K
2
Cr
2
O
7
50-100 PbCr
2
O
7

Trng Pb(CH
3
COO)
2
10-50 Na
2
SO
4
10-50 PbSO
4

Vang anh Na
2
SO
3
10-50 KMnO
4
10-50 MnO
en Co(CH
3
COO)
2
10-100 KMnO
4
15-25 CoO


Bang 7.5. Thanh phn dung dch khi nhum mau cac hp cht hu c.
Tn cht mau Nng (g/l) pH Nhit (
o
C)
Alizarin vang 5 50
Vang da cam cho nhm 1-3 4-5 20-25
Mau tm cho nhm 1 4-7 50-60
Vang 53 cho nhm 1 6-7 50-60
Xanh cho nhm 1 3-4 50-60
Alizarin o 2 50-60

1.2.4. So d mach:


+ -






H
2
SO
4

Pb
Pb
R A
Al


Hnh 7.3.
II. Pht phat hoa kim loai:
La tao trn b mt kim loai mang pht phat khng tan bam chc vi kim
loai nn. Mang pht phat khng chu c trong dung dch axit va kim manh.
nhit cao (400-500
o
C) mang pht phat cung khng chu c lu.
2.1. Pht phat hoa nong:
2.1.1. Pht phat hoa thuong:
Nhung mu thep vao dung dch mui pht phat dang hoa tan, thng s
dung la mui Majef: Mn(H
2
PO
4
)
2
.H
2
O, Mn(HPO
4
), Fe(H
2
PO
4
)
2
hay monophotphat
Zn. Co dang tng quat nh sau: Me(H
2
PO
4
)
2

Mui nay nhit thng b phn huy nhng khng ang k:

4 3 4 2 4 2
) ( ) ( PO H HPO Me PO H Me + (1)
un nong se phn huy trit hn:
4
4 3 2 4 3 4 2 4 2
5 ) ( ) ( ) ( PO H PO Me HPO Me PO H Me + + (2)
Khi nhung thep vao dung dch pht phat se xay ra hai qua trnh sau:
* Qua trnh ant:
+

2
Fe Fe
* Qua trnh catt:
2
2 2 H e H +
+
Ion H
+
do s phn li cua H
3
PO
4
t do hay do cac phan ng sau:
(3)
+
+
4 2
2
2 4 2
2 ) ( PO H Me PO H Me
(4)
+
+
2
4 4 2
HPO H PO H
(5)
+
+
3
4
2
4
PO H HPO
Kt qua la lp dung dch gn sat b mt mu thep giau ion Fe
2+
cung nh
cac ion HPO
4
-
va PO
4
3-
. Tch s tan cua FeHPO
4
, MnHPO
4
, cung nh Fe
3
(PO
4
)
2
,
Mn
3
(PO
4
)
2
rt nho. Do vy, lp dung dch gn sat b mt mu thep at n qua bao
hoa va kt tinh ln b mt thep tao thanh lp phu pht phat theo phan ng:
(6)
4
2
4
2
FeHPO HPO Fe = +
+
Mn (7)
4
2
4
2
MnHPO HPO = +
+
(8)
4
2
4
2
ZnHPO HPO Zn = +
+
3 (9)
2 4 3
3
4
2
) ( 2 PO Fe PO Fe = +
+
3 (10)
2 4 3
3
4
2
) ( 2 PO Mn PO Mn = +
+
3 (11)
2 4 3
3
4
2
) ( 2 PO Zn PO Zn = +
+
Thi gian pht phat hoa khoang 35-50 phut, nhit dung dch duy tr
khoang 96-98
o
C. Nhit cao, mui se b phn huy theo phan ng (1) va (2). Do
o, MeHPO
4
va Me
3
(PO
4
)
2
co th kt tua ln b mt thep va ca ngoai dung dch.
Ngc lai, nu nhit thp th thi gian pht phat hoa se keo dai.
Thi gian, chiu day, cu truc cua lp pht phat hoa phu thuc vao cac yu
t sau:
- Kim loai.
- Phng phap gia cng b mt trc khi pht phat hoa.
- Nhit .
- Tap cht co trong dung dch (SO
4
2-
, Cl
-
)
- T s axit chung va axit t do.
D axit tu do c xac nh bng phep chun vi metyldacam. C
10ml dung dch th mt 3-4ml NaOH 0.1N
D axit chung c xac nh bng phep chun vi phenolphtalein.
C 10ml dung dch th mt 28-30ml NaOH 0.1N
Lng dung dch NaOH 0.1N chun nay c biu th bng im. V vy,
ch s axit chung 28-30 im va ch s axit t do 3-4 im.
1hanh phn va ch d lam vic:

Majef 32g/l
Nhit 98-100
o
C
Thi gian 40-65 phut
Axit chung/Axit t do 7-8
2.1.2. Pht phat hoa nhanh:
giam thi gian pht phat hoa xung con 10-15 phut, ngi ta thm vao
dung dch pht phat cac cht kh phn cc: mui bisunphit, sunphit hay cac hp
cht hu c: hydroxylamin, nitrobenzen, thioure'.
2.2. Pht phat hoa lanh:
La pht phat hoa nhit thng, khng tn nhit nng, khng cn khng
ch nhit mt cach nghim ngt. Tuy nhin, mang pht phat thu c mong
thng c dung lam nn cho lp sn.
1hanh phn va ch d lam vic:

Dung dch 1:
Majef 35-45g/l
Zn(NO
3
)
2
70-90g/l
NaF 4-6g/l
Thi gian 20-40 phut
Axit chung/Axit t do 10-13
Dung dch 2:
H
3
PO
4
35-45g/l
ZnO 15-17g/l
NaNO
2
4-6g/l
Thi gian 15-20 phut
pH 2-3






PHU LUC

DON VJ & CACH TINH TC D N MON:
Tc n mon c tnh bng mils (1mils 0.001 inch; 1inch 2.54cm)
tc la mc xuyn thung trn mt nm (MPY: penetration per year) co th
tnh theo cng thc sau:

T A D
W
MPY


=
534
(cm/h)
534: hng s
W: khi lng mt i (mg)
D: t khi (g/cm
3
)
A: din tch mu (cm
2
)
T: thi gian (h)

1MPY 0.0254 mm/nm 25.4 m/nm 2.90 nm/h 0.805 pm/s
1m 10
3
mm 10
6
m 10
9
nm 10
12
pm

Bang 8.1. bn n mon
D bn n mon MPY
Khng b n mon <1
c bit 1-5
Tt 5-20
Kha tt 20-50
Kem 50-200
Khng chp nhn c >200































1AI LIU 1HAM KHAO:

1/ W.A. SChultze; Phan Lng Cm. n mon & bao v kim loai. 1985.
2/ Nguyn nh Luyn. n mon va bao v kim loai. NXB Cng nhn ky thut,
1980.
3/ Nguyn nh Ph. n mon va bao v kim loai. NXB T.P. H Ch Minh, 1980.
4/ Nguyn vn Tu. n mon va bao v kim loai. NXB Khoa hoc ky thut, 2001.
5/ H.H. VHLIG. Corrosion and corrosion control. New York, 1971.
6/ L.L. SHREIR. Corrosion I and II. London, 1976.
7/ DENNY A. JONES. Principle and prevention of Corrosion. New York, 1992.
8/ B. COTTIS. Introduction to corrosion. 2002.
9/ M. Pourbaix. Atlas of Electrochemical Equilibria in aqueous Solution. Oxford,
1966.
10/ http://www.cp.umist.ac.uk/CPC/Courses
11/ http://www. umist.ac.uk/corrosion/lecturenotes/Echem





























MUC LUC

CHNG 1: M U
I. Tnh hnh n mon va bao v kim loai cua th gii va Vit Nam.
II. ai cng n mon
2.1. nh ngha
2.2. Phn loai

CHNG 2: N MON IN HOA
I. Khai nim
1.1. Gii thiu
1.2. Phan ng in hoa
1.3. nh lut Faraday
II. in th in cc
2.1. Lp in tch kep
2.2. Nguyn nhn xut hin lp in tch kep
2.3. Cac loai in cc so sanh
III. Phng trnh ng hoc c ban cua qua trnh in cc
3.1. Nng lng hoat hoa t do
3.2. Qua trnh phn cc hoat hoa trang thai cn bng
3.3. Qua trnh phn cc hoat hoa trang thai khng cn bng
IV. ng hoc cac qua trnh in cc
4.1. Phan ng in cc b khng ch bi giai oan chuyn in tch
4.2. Phan ng in cc b khng ch bi giai oan khuch tan
4.3. S phn cc lin hp

CHNG 3: LY THUYT N MON HN HP

I. Co cu n mon din hoa
II. iu kin nhit ng cua qua trnh n mon
III. n mon vi s kh phn cc hydro va oxy
3.1. n mon vi s kh phn cc hydro
3.2. n mon vi s kh phn cc oxy
IV. Ly thuyt in th hn hp


CHNG 4: GIAN IN TH - pH (GIAN POURBAIX)

I. Gioi thiu
II. Gian E-pH cua nc sach 25
o
C
III. Gian E-pH cua h Fe-H
2
O 25
o
C
IV. Cng dung cua gian E-pH

CHNG 5: THU NG HOA VA PHNG PHAP BAO V IN HOA

I. Thu ng hoa kim loai
1.1. Khai nim
1.2. ng hoc cua qua trnh thu ng hoa kim loai
1.3. Bao v ant
II. Bao v in hoa bng cach thay i in th in cc
2.1. Khai nim
2.2. Bao v bng Protector
2.3. Bao v bng dong in ngoai

CHNG 6: NHNG NHN T ANH HNG N TC N MON

I. Nhng nhn t bn trong
1.1. Tnh bn nhit ng cua kim loai
1.2. V tr cua kim loai trong bang h thng tun hoan
II. Nhng nhn t bn ngoai
2.1. Anh hng cua pH
2.2. Anh hng thanh phn va nng cua dung dch mui
2.3. Anh hng cua nng oxy
2.4. Anh hng cua nhit
2.5. Anh hng cua tc chuyn ng cua dung dch
2.6. Anh hng cua dong in ro
2.7. Anh hng cua cac nhn t khac
III. Cht lam chm n mon
3.1. Khai nim
3.2. Cht lam chm ant
3.3. Cht lam chm catt
3.4. Cht lam chm hu c
3.5. Cht lam chm bay hi
3.6. Cht lam chm hoa tan trong du m

CHNG 7: LP PHU BAO V

A. Lop phu kim loai
I. C cu
1.1. Lp phu ant
1.2. Lp phu catt
II. Phng phap phu
2.1. Phng phap in
2.2. Phng phap nhit
B. Lp phu phi kim loai
I. Trang men
1.1. C cu bao v cua lp men
1.2. Nguyn liu san xut men
1.3. Trang men
II. Sn
2.1. Vai tro cua lp sn
2.2. Yu cu cua mang sn
2.3. Thanh phn cua mang sn
2.4. Qua trnh gia cng mang sn
C. Lp phu cac hp cht yhoa hoc
I. Oxy hoa va nhum mau kim loai
1.1. Oxy hoa kim loai en
1.2. Oxy hoa kim loai mau
II. Pht phat hoa kim loai
2.1. Pht phat hoa nong
2.2. Pht phat hoa lanh






































LI GII THIU

n mon va bao v kim loai la mt nganh khoa hoc co lin quan n nhiu
lnh vc khac nhau: kim loai hoc, hoa l, hoa phn tch, hoa polimer, hoa mi
trng, hoa silicat .... Giao trnh c soan thao ngn gon, suc tch nhm giup cho
giao vin va sinh vin d oc va nm bt c vn mt cach d dang. Nhn
chung, cac chng c thit k t phn nh tnh, m ta bao gm nguyn l va cac
tnh cht nhit ng n phn nh lng bao gm cac phng phap ngn can va
cac phng phap kim tra. c bit, phn cui cung cp n mt s ng dung
mang tnh thc t cao. Tht vy, giao trnh nay co th cung cp thng tin cho ban
oc mt s kin thc mong mun.
Mt s kin thc v in hoa a c trnh bay kha chi tit trong cac
chng 2, chng 3 va chng 4, nhm giup cho sinh vin co mt cng cu
nghin cu v nhng vn phn tch va bao v kim loai khoi n mon. Chng 5
cp n vn thu ng hoa kim loai va cac phng phap in hoa chng n
mon. Chng 1 gii thiu tng quan v cac dang n mon thng gp trong thc t.
Hai chng cui cp n cac nhn t anh hng n tc n mon va mt s
phng phap co hiu qua c s dung chng n mon trong thc t.
Giao trnh nay khng phai la mt cm nang cho vn n mon va chng n
mon. iu cn nhn manh la cp n nguyn l va mt s phng phap a c
nghin cu lam giam tnh n mon cua kim loai trong thc th cng nghip hin
nay. Tht vy, muc ch cua giao trnh nay nhm gii thiu mt cach khai quat v
nguyn ly va cach phong chng n mon kim loai cho cac sinh vin khng thuc
chuyn nganh in hoa va n mon kim loai cac trng ai hoc va Cao ng ky
thut cac nm th hai va th ba hoc co th lam c s cho cac ngi bt u
nghin cu v nganh khoa hoc nay.
Tac gia xin chn thanh cam n B mn Cng ngh hoa hoc, Khoa Hoa ky
thut, lanh ao trng ai Hoc Bach Khoa a Nng cung nh ai Hoc a Nng
a tao moi iu kin thun li trong qua trnh bin soan va xut ban giao trnh nay.
Tuy vy, giao trnh nay con rt nhiu khim khuyt, rt mong c s gop
y cua cac c gia c bit la cua ng nghip, sinh vin va cac nha nghin cu
trong lnh vc n mon va chng n mon giao trnh ngay mt hoan thin hn.
Xin chn thanh cam n.
a Nng, ngay 20 thang 06 nm 2003
ThS. L NGOC TRUNG

CHUO^G 1
MO DU
I/ Tinh hinh n mon va bao v kim loai cua th gioi va Vit Nam.
II/ Dai cuong n mon:
3. Djnh ngha:
n mon kim loai la s t pha huy kim loai do tac dung hoa hoc va in hoa
gia chung vi mi trng bn ngoai.
Noi mt cach khac n mon la qua trnh chuyn bin kim loai t dang nguyn t
thanh dang hp cht. S n mon thng bt u xay ra trn b mt kim loai, ri
qua trnh phat trin vao su kem theo s bin i thanh phn va tnh cht hoa l cua
kim loai va hp kim. Kim loai co th hoa tan mt phn hay toan b tao ra cac san
phm n mon di dang kt tua trn b mt kim loai (lp g, oxyt, hydrat, ...)
4. Phn loai
2.1. Theo co cu cua qua trinh n mon
- n mon hoa hoc
- n mon in hoa
2.4. Theo diu kin cua qua trinh n mon
- n mon kh
- n mon kh quyn
- n mon trong cht in giai
- n mon trong t
- n mon do dong in ngoai
- n mon do tip xuc
- n mon do ng sut
- n mon do vi sinh vt
2.5. Theo dc trung cua dang n mon (Hinh 1.1)
- n mon u (thep cacbon trong dung dch axit sunphuaric)




- n mon khng u (thep cacbon trong nc bin)



- n mon chon la, tc ch mt pha b pha huy (gang trong axit)




- n mon vt, tao thanh nhng vt dai trn b mt (ng thau trong nc
bin)



- n mon h (n mon trong t)




- n mon im, ng knh t 0.1 2 mm (thep khng g trong nc bin)




- n mon di b mt




- n mon gia cac tinh th (thep crom 500
o
C 800
o
C)




- n mon nt, do tac ng ng thi gia n mon va c hoc (n mon canh
tuc bin)



Hnh 1.1

CHUO^G 2
N MON DIN HOA

I/ Khai nim
1.1. Gioi thiu:
Khi nghin cu s lam vic cua pin Cu-Zn trong dung dch in giai nao o
ta thy pha Zn mon dn do hin tng hoa tan. Nh vy Zn ong vai tro anod
trong pin Cu-Zn. Cac phan ng in cc xay ra nh sau:
Cu ) ( ) ( ) ( ) (
2 2
l Zn r Cu r Zn l
+ +
+ +
Zn ZnSO
4
CuSO
4
Cu (r)
Qua trinh anod Cu ni Qua trinh catod


Zn(r) Zn
2+
(l) Cu
2+
(l) Cu (r)

Trong thc t qua trnh n mon xay ra trn cung mt kim loai, ngha la trn
o ng thi xay ra qua trnh anod va catod, a n s pha huy kim loai.
K


A K A A
Hnh 2.1.
1.2. Phan ung din hoa:
Ky thut in hoa c s dung rng rai trong k thut va i sng. Tuy
nhin, trong n mon va trong nganh ma in vn cn quan tm o la c tnh
cua b mt phn pha gia kim loai-dung dch: v du, tc phan ng tai b mt,
tnh cht cua lp mang trn b mt hoc hnh dang cua b mt. Cng cu khao
sat va nghin cu cac tnh cht trn la th va dong. T hai thng s nay chung ta
co th suy lun moi th co th xay ra trn b mt phn pha. Khi chung ta nhung
mt thanh kim loai vao dung dch in li, th kim loai co khuynh hng phan ng
vi dung dch in li o: kim loai co th hoa tan tao thanh cation hoc cac
cation trong dung dch co th kt tua thanh kim loai:
V du: e Fe Fe 2
2
+
+
Hoc Fe e Fe +
+
2
2
Kt qua cua nhng phan ng nay la kim loai co khuynh hng tch tu in
tch m hoc dng. S tch tu nhng in tch nay se lam thay i in th cua
kim loai va in th se at n gia tr khi tc cua hai phan ng at cn bng.
in th nay goi la in th cn bng.
Mt iu quan trong, khi cho mt manh kim loa vao dung dch in li
in th cn bng cua no, iu nay khng co nghia la tc hoa tan kim loai va
phan ng kt tua kim loai la bng khng. Phan ng in hoa lun lun la mt qua
trnh chuyn in tch, chung ta co th nh ngha tc cua cac phan ng nay
bng mt dong. Khi tc phan ng hoa tan kim loai bng tc phan ng kt
tua kim loai th chung ta co th nh ngha tc cua cac phan ng nay bng mt
dong trao i.
Trong n mon kim loai co hai phan ng quan trong khac la phan ng kh
oxy hoa tan tao thanh ion hydroxyl va phan ng kh ion hydro hoc phn t
nc tao thanh kh hydro:

+ + OH e O H O 4 4 2
2 2

2
2 2 H e H +
+

+ + OH H e O H 2 2 2
2 2
S cn bng gia mt hoc nhiu phan ng catod vi phan ng anod hoa
tan kim loai th ta xac nh c mt dong n mon. Mt trong nhng ng dung
phng phap in hoa nghin cu n mon la xac nh ln cua mt dong
n mon va c ch cua qua trnh n mon.
1.3. Djnh lut Faraday:
Cac phan ng in hoa hoc san xut ra electron hoc tiu thu electron.
Dong electron c o bng dong I (A). Theo nh lut Faraday t l gia khi
lng cht phan ng m, vi dong I, c xac nh nh sau:

nF
Ita
m = (1)
F: hng s Faraday (=96500 coulomb)
n: s electron trao i
a: khi lng nguyn t
t: thi gian
Chia phng trnh (1) cho thi gian t va din tch b mt A, ta xac nh
c tc n mon r:

nF
ia
tA
m
= = r (2)
i: mt dong (
A
I
= i ).
Phng trnh (2) ch ra t l gia khi lng kim loai mt i trn mt n v
din tch trong mt n v thi gian (v du: mg/dm
2
/ngay) va mt dong I (v du:
mA/cm
2
).
II/ Din th din cuc:
2.1. Lop din tich kep:
Khi cho kim loai tip xuc vi cht in giai th xay ra s tac dung gia kim
loai vi cht in giai o. Trn gii han phn chia gia hai pha in cc-dung dch
se xut hin lp in tch kep (chiu day cua lp nay <0.1nm) va bc nhay th
c goi la in th in cc. Co nhiu l thuyt m ta cu truc cua lp in tch
kep nay nh l thuyt cua Helmholz, Gouy-Chapman va Gouy-Chapman-Stern.
2.2. Nguyn nhn xut hin lop din tich kep:
- Chuyn in tch t pha nay sang pha khac

+ -




e -
-
-
-
-
-
-
+ -
+ -
+ -
+ -
+ -
Hnh 2.2.
+
+
+
+
+
+
+
- Hp phu chon loc cac anion hay cac phn t lng cc trong dung dch









Hnh 2.3.
- Do hai nguyn nhn trn






Hnh 2.4.
-
-
-
-
-
-
-
+
+
+
+
+
+
+
2.3. Cac loai din cuc so sanh:
- in cc chun hydro (Standard Hydrogen Electrode: SHE)
Hay con c goi Normal Hydrogen Electrode: NHE
- in cc Calomel bao hoa (Saturated Calomel Electrode: SCE)
- in cc bac-clorua bac (Silver-Silver Chloride Electrode: Ag/AgCl)
III/ Phuong trinh dng hoc co ban cua qua trinh din cuc:
3.1. Nng luong hoat hoa tu do:
Xet mt in cc kim loai-ion kim loai ngha la in cc kim loai nhung
vao dung dch ch cha ion kim loai o. Trong trng hp nay cht kh (RED) la
nhng nguyn t kim loai trn b mt in cc, con cht oxy hoa (OX) la cac ion
kim loai trong dung dch:
Qua trnh oxy hoa: RED OX + ne (mt in t)
Qua trnh kh: OX + ne RED (nhn in t)
V du: Ag Ag
+
+ e
Kim loai Lop din tich kep Cht din li
G
(nng lng t do)

ion k.l. trong mang tinh th ion k.l. b hydrat hoa trong dung dch

*
G

*
G

Hnh 2.5
vi nFE G =
3.2. Qua trinh phn cuc hoat hoa o trang thai cn bng:
Nng lng hoat in hoa hoc i vi qua trnh chuyn in tch (k hiu
) cua mt phan ng in cc c xac nh bng tng cua:
_____
*
G
- Nng lng hoat hoa hoa hoc ( ) i vi phan ng catod:
*
c
G
OX + ne RED
hoc nng lng hoat hoa hoa hoc ( ) i vi phan ng anod:
*
a
G
RED OX + ne
- Hiu ng in trng trong lp kep, yu t nay se lam tng hay giam nng
lng hoat hoa vt qua hang rao th nng va no bng mt ai lng nFE.
: h s chuyn in tch, c a ra n gian vic tnh toan anh hng
cua in trng i vi hang rao th nng (t pha kim loai la , con v pha dung
dch la (1-). Thng thng nhng phng trnh c dung trong ng hoc n
mon th = 0.5).
Nh vy: = (1)
_____
*
a
G E nF G
a

*
va = (2)
_____
*
c
G E nF G
c
+ ) 1 (
*

Kim loai Lop din tich kep Cht din li
G
(nng lng t do)






_____
*
a
G
*
c
G
*
a
G E nF
_____
*
c
G
E nF ) (1

Hnh 2.6
Tc phan ng in cc hoan toan phu thuc vao tn s giao ng cua
cac ion co th vt qua hang rao th nng gia hai pha in cc-dung dch hoan
thanh phan ng chuyn in tich.
Da vao phng trnh Gibbs va nh lut Faraday ta co:
* i vi phan ng RED OX + ne (phan ng anod hay qua trnh oxy
hoa)
] exp[
______
*
RT
G
C nFf i
a
RED a a

= (3)
* i vi phan ng OX + ne RED (phan ng catod hay qua trnh kh)
] exp[ ) (
______
*
RT
G
C nFf i
c
OX c c

= (4)
Thay gia tr (1) va (2) vao (3) va (4) ta co:
]
) (
exp[
*
RT
E nF G
C nFf
a
RED a a

=

i (5)
}
] ) 1 ( [
exp{ )
*
RT
E nF G
C nFf i
c
OX c c
+
=

( (6)
hay ] exp[
'
RT
E nF
C nFf i
RED a a

=

(7)
}
) 1 (
exp{ )
'
RT
E nF
C nFf i
OX c c

=

( (8)
Vi ) exp(
*
'
RT
G
f f
a
a a

= va ) exp(
*
'
RT
G
f f
c
c c

=
trang thai cn bng ng: RED = OX + ne
Ta co:
0
) ( ) ( i i i
cb c cb a
= =
Nh vy, ta co:
}
) 1 (
exp{ ] exp[
' '
RT
E nF
C nFf
RT
E nF
C nFf
cb
OX c
cb
RED a

=

(9)

RED a
OX c cb
C f
C f
E
RT
nF
'
'
) = exp( (10)

RED
OX
a
c cb
C
C
f
f
E
RT
nF
ln ln
'
'
+ = (11)

RED
OX
a
c cb
C
C
nF
RT
f
f
nF
RT
E ln ln
'
'
+ = (12)
Phng trnh (12) co th vit di dang in th in cc, trong o E khac
vi E mt ai lng nao o:
RED
OX
a
c cb cb
C
C
nF
RT
f
f
nF
RT
E E ln ) ln (
'
'
+ + = + = (13)
C
OX
, C
RED
: nng cht oxy hoa va cht kh tai in cc trang thai cn bng.
iu kin chun: l mol C C
RED OX
/ 1 = =

0
E E
cb
= (in th in cc chun)

RED
OX cb
C
C
nF
RT
E E ln
0
+ = (14)
y chnh la phng trnh NERNST
3.3. Qua trinh phn cuc hoat hoa o trang thai khng cn bng:
Khi cn bng th tc anod bng tc catod. Khi cn bng in hoa b
pha v bng cach lam thay i nng lng t do cua cac cht phan ng n mt
gia tr khac, ngha la lam cho E E
cb
th luc o mt dong in anod hay catod
se c sinh ra do anh hng cua s di chuyn khoi gia tr E
cb
ti nng lng
hoat hoa cua phan ng catod hay anod. Trong trng hp nay ta co:
] exp[
' '
RT
E nF
C nFf i
RED a a

=

(15)
}
) 1 (
exp{ ) (
' '
RT
E nF
C nFf i
OX c c

=

(16)
' '
,
OX RED
C C : la nng cht kh va cht oxy hoa tai b mt in cc trang
thai khng cn bng
Phng trnh (15) va (16) co th vit lai nh sau:
]
) (
exp[
'
0
RT
E E nF
C
C
cb
RED
RED
a

i i = (17)
]
) ( ) 1 (
exp[ )
'
0
RT
E E nF
C
C
i i
cb
OX
OX
c

=

( (18)
Luc nay C : la nng cht kh va cht oxy hoa trong dung dch.
OX RED
C ,
Vi E - E
cb
= E - E
cb
= th luc nay mt dong in tng i
total
in
cc se la:
c a total
i i i + =
Hay ]}
) 1 (
exp[ ] exp[ {
' '
0
RT
nF
C
C
RT
nF
C
C
i i
OX
OX
RED
RED
total

= (19)
Phng trnh (19) la phng trnh c ban trong ng hoc cac qua trnh in
cc, no cho bit mi quan h gia tc phan ng i vi , C
RED
, C
OX
, i
o
, .
Nu nh qua trnh khuych tan nhanh th nng cac cu t phan ng tai
b mt in cc va trong th tch dung dch se nh nhau, co ngha la:
C va
RED RED
C =
'
OX OX
C C =
'
Nh vy phng trnh (19) se tr thanh:

]}
) 1 (
exp[ ] {exp[
0
RT
nF
RT
nF
i i
total

= (20)
Phng trnh nay c goi la phng trnh BUTLER-VOLMER. y la
phng trnh c ban cho tt ca cac qua trnh ng hoc cua phan ng in hoa.
IV/ Dng hoc cua cac qua trinh din cuc:
4.1. Phan ung din cuc bj khng ch boi giai doan chuyn din tich:
Nh a trnh bay, nu qua trnh khuych tan nhanh th nng cua cac cu
t phan ng xem nh bo qua. Luc o, tc cua qua trnh anod va catod nh sau
va c th hin bng 2 nhanh trn th i- (Hnh 2.7.)

RT
nF
i i
a

exp
0
= (21)
]
) 1 (
exp[
0
RT
nF
i i
c

= (22)


i=i
a
+ i
c
> 0

i
a



i
i
c



i=i
a
+ i
c
< 0
Hnh 2.7
* Qua th lon (trn th nu qua th dng ln th phan ng catod ring
phn co th bo qua va nu qua th m ln th phan ng anod ring phn co th bo
qua). Luc nay ta co:

a
a
a
RT
nF
i i

303 . 2
log log
0
+ = (>50mV) (22)

c
c
c
RT
nF
i i

303 . 2
) 1 (
log
0
log

= (> -50mV) (23)
Hay:
a
a a
i
nF
RT
i
nF
RT
log
303 . 2
log
303 . 2
0

+
a
= (24)

c
c c
c
i
nF
RT
i
nF
RT
log
) 1 (
303 . 2
log
) 1 (
303 . 2
0

= (25)
Dang tng quat:
i b a log + = (26)
Phng trnh (26) goi la phng trnh Tafel (Hnh 2.8). dc cua ng
thng ) (logi c goi la dc Tafel, c dung xac nh cac thng s ng
hoc cua qua trnh chuyn in tch i
o
, .
Vi
nF
RT
b
a
a

303 . 2
= va
nF
RT
c
c
) 1 (
303 . 2

= b


i
a


i
o




i
c


logi
Hnh 2.8
* Qua th nho, va gia su rng
a

c
0.5
Ta co:
RT
nF
i i
0
= (27)
Do o, ta co in tr phn cc R
p
:

0
nFi
RT
i
R
p
= =

(28)
Thay bng gia tr cua dc Tafel ta co:

p c a
c a
R b b
b b
i
) ( 303 . 2
0
+
= (29)
Phng trnh (29) c goi la phng trnh Stern-Geary.
Chu y: gia tr b
c
trn c ly gia tr dng cho tng quat hoa. Thc ra b
c

mang gia tr m, va do o phn b chia trong phng trnh Stern-Geary phai la
2.303(b
a
-b
c
)R
p

4.2. Phan ung din cuc bj khng ch boi khuych tan:
Tc phan ng in cc cung co th b khng ch bi s vn chuyn cua
cac cu t phan ng n va i khoi b mt in cc. S chuyn vn nay co th do:
- S in di (do gradient in th gy ra): co th loai tr.
- S khuych tan (do gradient nng gy ra)
- S i lu (do gradient tc gy ra)
Gia s xet mt phan ng in cc trn o xay ra qua trnh kh:
2H
+
+ 2e H
2

S dung m hnh NERNST (Hnh 2.9.):
Nng
C
0
2
H


0
)
= x
dx
dC
(


'
C
2
H


khoang cach x
Hnh 2.9.
: nng ion H
0
2
H
C
+
trong dung dch
: nng ion H
'
2
H
C
+
trn b mt in cc
: chiu day lp khuych tan
S dung m hnh Nernst, cac nh lut Fick, va nh lut Faraday ta co:
) 1 log(
303 . 2
L
c
c
i
i
nF
RT
=
4.3. Su phn cuc lin hop:
Tng qua trnh phn cc catod (k hiu
T,c
) la tng cua qua trnh phn cc
hoat hoa va phn cc nng :

conc c act c T
+ =
, ,

vi
0
0 ,
log log
) 1 (
303 . 2
log
) 1 (
303 . 2
i
i
b i
nF
RT
i
nF
RT
c
c c
c c
c act
=

) 1 log(
303 . 2
L
c
conc
i
i
nF
RT
=

) 1 log(
303 . 2
log
0
,
L
c c
c c T
i
i
nF
RT
i
i
b + =


Con i phan ng anod hoa tan kim loai th phn cc nng xem nh
khng ang k (co th bo qua). Do o:


0
log
i
i
b
a
a a
=

nhanh anod (chuyn in tch khng ch)



i
L


i

nhanh catod
(chuyn in tch khng ch)


nhanh catod
(khuych tan khng ch)
Hnh 2.10.


























CHUO^G 3
LY THUYT N MON HN HOP

I/ Co cu n mon din hoa:
Kim loai Cht din li
Vung anod




Vung catod



Hnh 3.1.
Me ne
ne D D.ne
Me
n+

A
-

K
+

Gm 3 qua trnh:
1. Qua trinh anod: ne Me Me
O mH
2
n+
.mH
2
O
2. Qua trinh chuyn din tu thua:
3. Qua trinh catod: D + ne [D.ne]

II/ Diu kin nhit dng cua su n mon:
iu kin h nhn co th trao i in t vi h cho khi:

cb
M
cb
R
E E >
: in th cn bng cua h nhn
cb
R
E
: in th cn bng cua h cho (kim loai)
cb
M
E
Ji du: cho thanh st nhung trong dung dch acid vi pH = 1,
, l mol C
Fe
/ 10
6
2

=
+
atm P
H
1
2
=
H cho: e Fe Fe 2
2
+
+

V E
C
nF
RT
E E
cb
Fe Fe
Fe Fe Fe
cb
Fe Fe
62 . 0 10 log 03 . 0 44 . 0
ln
6
/
0
/ /
2
2 2 2
= + =
+ =

+
+ + +

H nhn:
2
2 2 H e H +

+

V E
pH E
cb
H H
cb
H H
06 . 0
059 . 0
2
2
/
/
=
=
+
+
Vy , nn st b n mon va co kh hydro thoat ra.
cb
M
cb
R
E E >
III/ n mon voi su khu phn cuc hydro va oxy:
3.1. n mon voi su khu phn cuc hydro:
3.1.1. Diu kin nhit dng:
Nhng qua trnh n mon kim loai ma cht kh phn cc la ion H
+
va san
phm thoat ra catod la H
2
, th c goi la n mon kim loai vi s kh phn cc
hydro: O H H O H H e O H H
2 2 2 2
2
1
. + + +
+

iu kin c ban:
cb
M
cb
H
E E >
2
3.1.2. Qua trinh din cuc:
Gm 6 giai oan:
1/ Cac ion H+ b hydrat hoa tao thanh cac ion hydroxon va khuych tan n
b mt catod.
2/ Phong in cua ion hydroxon tao thanh ion hp thu:
O H H e O H H
hp 2 2
. + +
+
3/ Mt phn nguyn t hydro tao thanh hoa tan vao kim loai
4/ Kt hp cac nguyn t hp phu:
2
H H H
hp hp
= + hay kh hp phu in
hoa: O H H e O H H H
hp 2 2 2
. + + +
+
5/ Khuych tan cac phn t H
2
vao dung dch sau o khuych tan vao
khng kh.
6/ Cac phn t H
2
trn b mt catod tp hp lai thanh bot kh va thoat ra
khoi b mt kim loai:

2 2 2 2 2 2 2
.... nH H H H H H H = + + + + + +












Kim loai Khng khi


6 5

Dung djch

4

3
2
1

p
Hnh 3.2.
3.1.3. Dc dim cua su khu phn cuc hydro:
- n mon vi s kh phn cc hydro co kem theo s kh phn cc oxy.
- S kh phn cc hydro phu thuc nhiu vao pH.
- S kh phn cc hydro phu thuc voa b mt kim loai, cac tap cht.
- n mon vi s kh phn cc hydro co kem theo s don cua thep.
3.2. n mon voi su khu phn cuc oxy:
3.2.1. Diu kin nhit dng:
Nhng qua trnh n mon kim loai ma cht kh phn cc la oxy hoa tan
trong dung dch theo phan ng sau, goi la n mon kim loai vi s kh phn cc
oxy:

+ + OH e O H O 4 4 2
2 2
iu kin c ban:
cb
M
cb
O
E E >
2
3.1.2. Qua trinh din cuc:
Gm 6 giai oan:
1/ Oxy trong khng kh khuych tan vao dung dch qua b mt K-L
2/ Oxy hoa tan vao dung dch nh chuyn ng i lu t nhin hay cng
bc.
3/ Chuyn oxy qua lp Pran.
4/ Chuyn oxy qua lp khuych tan .
5/ Ion hoa oxy
* Trong mi trng trung tnh-kim:

+ + OH e O H O 4 4 2
2 2
* Trong mi trng acid:
O O H e H
2 2
2 4 4 + +
+
6/ Khuych tan ion OH
-
ra dung dch.

Kim loai Khng khi O
2

1


6
Dung djch
2

5

4 3


p
Hnh 3.3.
IV/ Ly thuyt din th hn hop:
n mon kim loai trong dung dch "nc" la kt qua cua 2 hay nhiu phan
ng in cc xay ra trn b mt kim loai, trong o co mt phan ng anod (oxy hoa
kim loai thanh ion cua no thanh dang oxyt hay hydroxyt), ng thi cung xay ra
mt hoc nhiu phan ng catod (kh cac cu t oxy hoa co mt trong dung dch).
Ly thuyt hn hp c cp trong phn nay i vi qua trnh n mon
kim loai trong mi trng acid, trung tnh hay kim yu. Cac v du sau se cho thy
tc n mon c quyt nh bi tc cua giai oan chm nht trong qua trnh
chuyn in tch hoc qua trnh khuych tan cua phan ng anod hay catod.
V du: Nhung mt thanh st sach vao dung dch acid (pH < 2)
Trong h nay co 5 phan ng in cc c xet n:
i
a,Fe

Fe Fe
2+
+ 2e (1)
i
c,Fe

i
c,H+

2H
+
+ 2e H
2
(2) (dd acid)
i
a,H+


i
c,H2O

2H
2
O + 2e H
2
+ 2OH
-
(2a) (dd trung tnh-kim)
i
a,H2O


i
c,O2

O
2
+ 4H
+
+ 4e 2H
2
O (3) (dd acid)
i
a,O2


i
c,O2

O
2
+ 2H
2
O + 4e 4OH
-
(3a) (dd trung tnh-kim)
i
a,O2


Theo quan im nhit ng hoc th phan ng (2) va (2a); (3) va (3a) la nh
nhau, chung co cung in th in cc cn bng.
Gia s rng dung dch a ui ht kh loai tr kha nng phan ng (3) va
(3a) xay ra. Ngoai ra phan ng (2a) co mt dong trao i thp. V vy, phan
ng kh nc kho co th xay ra. Nh vy, trong h st - acid trang thai n nh
ta co st b hoa tan va kh H
2
thoat ra:
O anod: i
a,Fe

Fe Fe
2+
+ 2e
i
c,Fe

O catod:
i
c,H+

2H
+
+ 2e H
2

i
a,H+


Hai phan ng nay xay ra ng thi trn cung mt b mt. Mi phan ng co
in th in cc va mt dong trao i ring (Hnh 3.4.).







E(V)
e H H 2 2
2
+
+
0.1 - i
+
H o,
0.0
cb
H H
E
2
/
+
2
2
2 H e H +
+



i Fe
Fe Fe / , 0
2+
e Fe 2
2
+
+

cb
E
/

Fe Fe
2+
- 0.5 -
Fe + Fe e
+
2
2

logi
Hnh 3.4.

Hai in th in cc va cung tn tai trn cung mt b mt
va ca hai phai phn cc n mt gia tr in th trung gian chung , goi la in
th n mon. c coi nh mt in th hn hp v no la in th in cc lin
kt cua hai in cc ring phn cua phan ng (1) va (2). Tai tc cua phan
ng anod (1) cn bng vi tc phan ng catod (2). Vy tc hoa tan anod i
xem nh tc n mon :
cb
H H
E
2
/
+
a c
i i
cb
Fe Fe
E
/
2+
corr
corr
E
corr
E
corr
E
a
corr
i i = = (Hnh 3.5.)












E(V)

+
i
H o,

cb
H H
E
2
/
+
2 +
+

2
2 H e H
i
corr M
E E =
corr
i
/

Fe Fe , 0
2+
e Fe Fe 2
2
+
+


cb
Fe Fe
E
/
2+

logi
Hnh 3.5
.
Vy )] ( exp[ ) (
, 0 ,
cb
Fe corr
Fe
Fe corr Fe a corr
E E
RT
nF
i i i = =


Va )] (
) 1 (
exp[ ) (
, 0 ,
cb
H
corr
H
H
corr
H c
corr
E E
RT
nF
i i i
+
+
+ +

= =


Phng trnh ng cong phn cc tng (Hnh 3.5.) cua phan ng n mon:

+
+ =
H c
Fe a total
i i i
,
,

Trong o:

)] ( exp[
)] ( exp[ )] ( exp[
)] ( ) ( exp[
,
, 0 ,
, 0 ,
corr
Fe
corr Fe a
cb
Fe corr
Fe
corr
Fe
Fe Fe a
cb
Fe corr corr
Fe
Fe Fe a
E E
RT
nF
i i
E E
RT
nF
E E
RT
nF
i
E E E E
RT
nF
i i
=
=
+ =

Tng t ta co: )] (
) 1 (
exp[
,
corr
H
corr
H c
E E
RT
nF
i i

=
+
+

: la gia tr phn cc cua in cc b n mon. K hiu .
corr
E E
Vy }]
) 1 (
exp{ [exp

RT
nF
RT
nF
i i
H Fe
corr total
+

=
` lon: tng t nh chng 2, ta co phng trnh Tafel dang tng quat
i a log + =
Vi
nF
RT
a
a

303 . 2
= va
nF
RT
c
c
) 1 (
303 . 2

=
` be: tng t nh chng 2, ta co:

RT
nF
i
corr
= i
hay
corr
i
i
nF
RT
=
Goi R
p
la in tr phn cc, ta co:

corr
p
nFi
RT
di
d
R = =
=0
) (

Thay bng gia tr cua dc Tafel ta co:

p c a
c a
corr
R
i
) ( 303 . 2

+
=

E(V)


cb
H H
E
2
/
+




Fe Fe
2
2 2 H e H +
+
corr
E
e 2
2
+
+



E
cb
Fe Fe /
2+
i
Hnh 3.6.











E(V)

+
i
H o,

cb
H H
E
2
/
+
2 +
+

2
2 H e H
i
corr
E
corr
i
/

Fe Fe , 0
2+
e Fe Fe 2
2
+
+


cb
Fe Fe
E
/
2+

logi
Hnh 3.7.
-1
-0.9
-0.8
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
0
-8 -7 -6 -5 -4 -3 -2 -1 0 1 2 3 4 5 6
x(i=10E+x)(mA/cm2)
E
(
v
o
l
t
)
H+->H2(M)
H+->H2(N)
sum(ic)
N->Nn+
M->Mm+
sum(ia)

Hnh 3.8.








CHUO^G 4
GIAN D DIN TH-pH (POURBAIX)

I/ Gioi thiu:
n mon kim loai trong dung dch "nc" la kt qua cua phan ng anod oxy
hoa kim loai cung vi mt hoc nhiu phan ng catod kh ion hydro hoc nc,
hoc oxy hoa tan. Vic xay ra cac phan ng ring phn nay phu thuc vao in th
cn bng cua anod va catod ring phn o: , , va .
cb
Me Me
n
E
/
+
cb
H H
E
2
/
+
cb
O H O
E
2 2
/
Theo phng trnh NERNST 25
o
C:
(1)
2
2
log 030 . 0 059 . 0
/
H
cb
H H
P pH E =
+
(2)
2 2 2 2 2
log 015 . 0 059 . 0
0
/ / O O H O
cb
O H O
P pH E E + =
Ca hai phng trnh trn u phu thuc vao pH va ap sut ring phn cua
kh tng ng.
Mt khac phan ng anod ring phn cung phu thuc vao pH:
Me + OH
-
Me(OH)
2
+ 2e
d dang khap sat mi quan h gia E-pH ta co th ve gian E-pH goi
la la gian POURBAIX.
Trn gian POURBAIX co 3 vung:
1/ Khi kim loai trang thai n nh v mt nhit ng, luc nay ta noi rng
kim loai se khng b n mon.
2/ Khi tao thanh cac san phm n mon co kh nng hoa tan, ta noi rng kim
loai trang thai hoat ng va tc n mon se tng manh.
3/ Khi tao thanh cac san phm n mon khng b hoa tan, ta noi rng kim
loai trang thai thu ng va tc n mon se xay ra chm.
II/ Gian d E-pH cua nuoc sach o 25
o
C:
Trong nc sach khi tip xuc vi khng kh, ngoai cac phn t H
2
O ra con
co mt lng rt nho ion H
+
va OH
-
, cung vi kh hoa tan ma quan trong la la kh
O
2
.
* i vi phan ng: 2H
+
+ 2e H
2

Phan ng trn cung co th vit lai di dang sau (trong mi trng trung tnh hay
kim)
2H
2
O + 2e H
2
+ 2OH
-
( E
H
0
) V
O H
83 . 0
/
2 2
=
theo phng trnh NERNST ta co: (ng a) at P
H
1
2
= pH E
cb
H H
059 . 0
2
/
=
+
* i vi phan ng: O
2
+ 4H
+
+ 4e 2H
2
O
( E
H
0
/
2
) V
O O
237 . 1
2
+ =
Phan ng trn cung co th vit lai di dang sau (trong mi trng trung tnh hay
kim)
O
2
+ 2H
2
O + 4e 4OH
-

( E
0
/

) V
OH O
411 . 0
2
+ =
theo phng trnh NERNST ta co: (ng b) at P
O
1
2
= pH E
cb
O
059 . 0 23 . 1
2
=
* i vi phan ng: H
+
+ OH
-
H
2
O
Vi hay 14 * =
+
OH H
C C 14 = + pH pOH
GIAN D E-pH CUA H2O
-2
-1.5
-1
-0.5
0
0.5
1
1.5
2
-2 0 2 4 6 8 10 12 14
pH
E
(
V
)
a
b
O
2

H
2

2H
+
+ 2e=H
2

O
2
+4H
+
+4e =2H
2
O
H
+
+ OH
-
=H
2
O
Hnh 4.1.
ng a va b chia gian thanh 3 vung. Vung trn cung ( in th cao)
nc co th b oxy hoa tao thanh oxy, vung thp nht ( in th thp) nc co th
b kh thanh hydro. Con vung gia (vung trung gian) ng vi trang thai bn cua
nc.
III/ Gian d E-pH cua h Fe-H
2
O o 25
o
C:
Ngoai cac cu t k n: H
2
O, H
+
, OH
-
, O
2
va H
2
, con phai k n cac
cu t khac nh: Fe, Fe
2+
, Fe
3+
, HFeO
2
-
, Fe(OH)
2
, Fe(OH)
3
.
Bang 4.1. ch ra nhng phan ng quan trong nht va cac phng trnh cn
bng iu kin:
V E V E
C C C C
l mol C C C
Fe Fe Fe Fe
OH Fe OH Fe
HFeO Fe Fe
77 . 0 ; 44 . 0
10 7 ) ( ; 10 9 . 1 ) (
; / 10
0
/
0
/
38 3 15 2
6
2 3 2
3 2
2
3 2
+ = =
= =
= = =
+ + +
+ +
+ +

Bang 4.1.
Phan ung Phuong trinh duong
e H H 2 2
2
+
+
pH E 059 . 0 =
a
e H O O H 4 4 2
2 2
+ +
+
pH E 059 . 0 23 . 1 + =
b
e Fe Fe 2
2
+
+

62 . 0 ) log( 0295 . 0 44 . 0
2
= + =
+
Fe E
1
e Fe Fe +
+ + 3 2
77 . 0 + = E 2
+ +
+ + H OH Fe O H Fe 2 ) ( 2
2 2
2
65 . 9 ) log( 5 . 0 65 . 6
2
= =
+
Fe pH
3
+ +
+ + H OH Fe O H Fe 3 ) ( 3
3 2
3

61 . 3 ) log(
3
1
613 . 1
3
= + =
+
Fe pH
4
e H OH Fe O H Fe 2 2 ) ( 2
2 2
+ + +
+
pH E 059 . 0 05 . 0 =
5
e OH Fe OH OH Fe + +

3 2
) ( ) ( pH E 059 . 0 27 . 0 + =
6
e H OH Fe O H Fe + + +
+ +
3 ) ( 3
3 2
2
pH E 177 . 0 41 . 1 + =
7
e H HFeO O H Fe 3 3 2
2 2
+ + +
+
pH E 0886 . 0 316 . 0 + =
8
+
+ H HFeO OH Fe
2 2
) ( 3 . 12 ) log( 3 . 18
2
= + =

HFeO pH
9
e OH Fe HFeO 2 ) (
3 2
+

46 . 0 ) log( 059 . 0 81 . 0
2
= =

HFeO E
10

ng 1 c tnh bng:
V Fe E E
Fe Fe
cb
Fe Fe
62 . 0 3 059 . 0 44 . 0 ) log(
2
059 . 0
2 0
/ /
2 2
= = + =
+
+ +

ng 5 c tnh nh sau:
T phan ng: (1) e Fe Fe 2
2
+
+
Ta co phng trnh: ) log(
2
059 . 0
2 0
/ /
2 2
+
+ =
+ +
Fe E E
Fe Fe
cb
Fe Fe

Vi phan ng: (2)
+ +
+ + H OH Fe O H Fe 2 ) ( 2
2 2
2
Ta co: T
2 2
) (
) )( (
2
+
= OH Fe
OH Fe
Cng phan ng (1) va (2) ta co phng trnh ng 5:
e H OH Fe O H Fe 2 2 ) ( 2
2 2
+ + +
+
Vi: ) log( 059 . 0
0
/ ) ( / ) (
2 2
+
+ = H E E
Fe OH Fe
cb
Fe OH Fe
V:
cb
Fe Fe
cb
Fe OH Fe
E E
/
/ ) (
2
2
+
=
Do o: )
) (
log(
2
059 . 0
2
/ ) (
0
/ /
2
2 2

+ =
+ +
OH
T
E E
Fe OH Fe
Fe Fe
cb
Fe Fe


2
/ ) (
0
/ /
) log( 059 . 0 ) log(
2
059 . 0
2
2 2

+ =
+ +
OH T E E
Fe OH Fe
Fe Fe
cb
Fe Fe

hay ) log( 059 . 0 14 059 . 0 ) log(
2
059 . 0
/ ) (
0
/ / 2
2 2
+
+ + + =
+ +
H T E E
Fe OH Fe
Fe Fe
cb
Fe Fe

Vy: 14 059 . 0 ) log(
2
059 . 0
/ ) (
0
/
0
/ ) (
2
2
2
+ + =
+
Fe OH Fe
Fe Fe
Fe OH Fe
T E E
Thay s vao ta co: 05 . 0
0
/ ) (
2
==
Fe OH Fe
E
Va phng trnh ng 5 nh sau: pH E 059 . 0 05 . 0 =
Gian d E-pH cua h Fe-H2O
2
HFeO2-
Fe
Fe2+
Fe3+
7
2
5
8
1
4
a
3
Fe(OH)3
Fe(OH)2
10
6
b
9
-1.5
-1
-0.5
0
0.5
1
1.5
2
2 4 6 8 10 12 14
pH
E
(
V
)

IV/ Cng dung cua gian d E-pH:
1/ Gian E-pH cua h kim loai-nuoc co 3 vung c trng:
a/ Vung kim loai cn bng vi ion kim loai nng 10
-6
mol/l.
Theo quan im n mon vung nay c goi la vung an toan.
b/ Vung hydroxyt kim loai (hay oxyt kim loai) cn bng vi ion kim
loai co nng 10
-6
mol/l. Vung nay thng kt tua day c va c goi la vung
thu dng.
c/ Vung kim loai hay hydroxyt kim loai (oxyt kim loai) cn bng vi
ion kim loai co nng 10
-6
mol/l. Vung nay xay ra cac phan ng n mon va
c goi la vung n mon.
2/ Trong mt gii han nao o, gian POURBAIX c a ra d oan
n mon. Tuy nhin, trn gian POURBAIX khng cho bit g v tc n mon
va ban cht bao v cua lp hydroxyt hay oxyt tao thanh trong vung thu ng.
3/ V nguyn tc co 3 phng phap chng n mon c rut ra t gian
POURBAIX:
a/ in th in cc co th lam m hn so vi in th n mon va
in th o kim loai nm trong vung an toan. Phng phap nay goi la bao v catod
(phn cc catod).
b/ in th in cc co th lam dng hn so vi in th n mon va
in th o kim loai nm trong vung thu ng. Phng phap nay goi la bao v
anod (phn cc anod).
c/ Co th chuyn pH sang phai cho kim loai ri vao vung thu
ng. Ngha la thay i mi trng co th dn n ngng n mon.

























CHUO^G 5
THU DNG HOA VA PHUONG PHAP BAO V DIN HOA

I/ Thu dng hoa kim loai:
1.2. Khai nim:
- Trang thai thu ng cua kim loai hay hp kim la trang thai ma trn b mt
cua no hnh thanh mt lp mang mong co tnh cht bao v kim loai hay hp kim
trong dung dch n mon. Lp mang nay co th day vai A
o
n vai trm A
o
va c
hnh thanh do qua trnh oxy hoa.
V du: e H OH Fe O H Fe 2 2 ) ( 2
2 2
+ + +
+
- c trng cho trang thai thu ng la khi kim loai b thu ng th in th
in cc cua no chuyn v pha dng hn (phn cc anod ln) va in tr n mon
ln, nn tc n mon giam nhanh.
- Hin tng thu ng do Lomonoxov tm ra nm 1738 va sau o c
Faraday phat trin thm vao nm 1840, khi ng nghin cu s n mon Fe trong
dung dch HNO
3
.
Tc n mon (g/m
2
.h)

1000 -



500 -



10 20 30 40 50 HNO
3
(%)
Hnh 5.1.
- Co hai cach chuyn kim loai vao trang thai thu ng:
* Phn cc anod (bng dong ngoai)
* Nhung vao dung dich in li co cha cu t thch hp.
1.2. Dng hoc cua qua trinh thu dng kim loai:
Gia s rng co mt s kim loai trong dung dch in li mt in th u
dng se xay ra phan ng sau:
(1) ye yH O Me O yH xMe
y x
2 2
2
+ + +
+
a/ Phn cuc anod:
V du: Fe b phn cc anod trong dung dch 0.5M H
2
SO
4
, bt u phn cc
t in th n mon E
corr
. (Hnh 5.2.)
E(V)
2 e H O O H 4 4
2 2
+ +
+
1.25 -

1.00 -
2 2
/ 10 7 m A i
pass

=


2 e H O Fe O H Fe 6 6 3
3 2 2
+ + +
+
+0.5 -


2 i =
2 3
/ 10 m A
cit

0.0 - FeSO
cb
H
E
2
2
2 2 H e H +
+
4

-0.25 -

-0.5 -
cb
Fe
E e Fe Fe 2
2
+
+
! ! ! !
-2 0 2 4 logi
Hnh 5.2.
b/ Nhung kim loai vao cht din li co cht oxy hoa thich hop:
Mun thu ng mt kim loai Me nao o th em nhung no vao trong dung
dch in li co cha cac cu t oxy hoa cua h oxy hoa kh (redox) co in th cn
bng dng hn . Trong trng hp ta co mt phan ng a in cc vi
in th hn hp ( ) c xac nh bng phan ng anod cua kim loai hoc oxyt
kim loai vi phan ng kh cua cht oxy hoa.
cb
redox
E
p
E
corr
E
Nu tc cua phan ng kh E ln hn tc phan ng anod ( i ) th
kim loai se b thu ng.
p crit
Cac iu kin thu ng kim loai bng h oxy hoa kh. H oxy hoa kh
thch hp cho s thu ng kim loai cn co nhng yu cu sau:
1/
cb
puqtd
E > (5a)
p
cb
redox
E E >
2/
crit redox c
i
p
>
,
E
i (5b)
Trong thc t cac h oxy hoa kh ap ng iu kin (5a), (5b) co th c
dung nh mt cht c ch thu ng trong dung dch n mon, chng han nh
Na
2
CrO
4
. Mt khac, nhng kim loai hoan toan b thu ng co th co hin tng n
mon cuc b. Hin tng nay la do s pha huy cuc b mang thu ng hoc bng
hoa hoc hoc bng c hoc. V du nh s pha huy mang thu ng bng cac yu t
hoa hoc do anh hng cua cac ion halogen c bit la Cl
-
, Br
-
, I
-
co mt trong mi
trng.
E(V)
Vung qua thu ng

cb
puqt
E

vung thu ng

cb
redox
E
corr
E
OX RED + ne

F
E
p
E vung chuyn tip

vung hoat ng
ne Me Me
n
+
+


logi
pass
logi
crit
logi
c,redox
logi
Hnh 5.3.
1.3. Bao v anod:
Trn c s phn tch s lam vic cua h thng n mon ta co th kt lun
rng nhiu trng hp kim loai b thu ng co th nng cao bn cua no bng
cach chuyn in th in cc v pha dng hn. Mun thc hin iu nay ta ni
kim loai cn bao v vi cc dng cua ngun mt chiu hay ni kim loai cn bao
v vi kim loai co in th in cc dng hn. Nhng hin nay vic ng dung
bao v anod vao thc t con nhiu han ch. Phng phap bao v anod chu yu
nng cao bn cua thep cacbon, thep khng g, hay titan trong mt s mi trng
nh xut c, axit sunphuaric co nng cao.
Dong bao v phai duy tr thng xuyn khi dong in chnh b ngt th phai
co dong phu.
Mun tin hanh bao v anod phai tun theo cac iu kin sau y:
- Trong mi trng o kim loai phai co kha nng thu ng khi phn cc
anod.
- Dong in be khi duy tr trang thai thu ng am bao bn n mon
cao, tiu hao nng lng t. Tuy nhin luc u phai cn mt dong ln vt
qua dong gioi han n vung thu ng cua kim loai.
- am bao co dong in thng xuyn khi bao v anod.
- vung in th hiu qua phai ln.
1uy nhin vic bao v anod thuong gp mt s kho khn nhu sau:
- Bao v anod khng thc hin c phn kim loai khng tip xuc vi
dung dch.
- Dong in ban u cho s thu ng anod ln nn cn phai co dung cu
khng ch in th va duy tr dong in.
- Rt kho khn bao v cho cac ng ng dn dai.
- Trong dung dch co cha cac ion hoat ng nh Cl
-
, th phai dung n ap
khng ch in th in cc cua kim loai vung thu ng nhng phai di in
th n mon l.
II/ Bao v din hoa bng cach thay di din th din cuc:
2.1. Khai nim:
Da trn th ng cong phn cc trong iu kin nao o ta co th
chuyn in th in cc v pha dng hn hay m hn so vi in th n mon th
dong in n mon co th giam. Nh vy, bao v in hoa la phn cc hoa in cc.
a/ Phn cuc anod:
Chuyn in th in cc v pha dng hn so vi in th n mon cho
n khi kim loai ri vao trang thai thu ng. Mun thc hin iu nay ta ni kim
loai cn bao v vi cc dng cua ngun mt chiu hay ni kim loai cn bao v
vi kim loai co in th in cc dng hn. Trong ca hai trng hp kim loai cn
bao v ong vai tro la anod. Cho nn tc n mon ch giam khi mi trng o
kim loai b thu ng.
b/ Phn cuc catod:
Chuyn in th in cc v pha m hn so vi in th n mon th hu
nh phan ng hoa tan kim loai ngng hn. Mun thc hin iu nay ta ni kim loai
cn bao v vi cc m cua ngun mt chiu hay ni kim loai cn bao v vi kim
loai co in th in cc m hn. Trong ca hai trng hp kim loai cn bao v u
ong vai tro catod, nn tc n mon se giam.
* Phn cc catod bng cach ni kim loai cn bao v vi cc m cua ngun mt
chiu, c goi la bao v catod din phn.
* Phn cc catod bng cach ni kim loai cn bao v vi kim loai khac co
in th in cc m hn, c goi la bao v bng Protector (anod hy sinh).
2.2. Bao v bng Protector:
Bao v bng Protector co th thc hin bng hai cach (Hinh 5.4.)

4




2

1


Gian tip Truc tip
1. Thit b cn bao v; 2. Protector Zn; 3. Cht boc Protector; 4. Dung cu kim tra
Hnh 5.4.
2.3. Bao v catod bng dong din ngoai:
Bao v catod bng dong ngoai co th lp t nh sau (Hinh 5.5.)

- +
4




5

Hnh 5.5.


3
V
1
A
3

3 2
1
1. Kim loai cn bao v 2. Anod phu 3. Cht boc
4. Ngun in mt chiu 5. in cc so sanh
Anod phu c ch tao t thep ph liu, re tin. Tuy nhin thng s dung
anod phu la in cc khng tan.
Mt s vt liu c dung lam anod phu nh sau (Bang 5.1.)
Bang 5.1.
Loai vt liu Dong cuc dai (A/m
2
) Dung luong (kg/A.nm)
Thep ph liu 5 10
Gang 35 0.1
Graphit 20 0.5
Ch (1%Ag; 6%Sb) 150 -
Ti
Ta + Pt
Nb

10.000

-

Tom lai, chon cach bao v bng protector hay bng dong ngoai phu thuc
chu yu vao cng trnh cn c bao v. i vi cng trnh nho phng phap dung
protector kinh t hn. Phng phap nay co u im la in th bao v phn b u.
Bao v catod bng dong ngoai c dung bao v nhng din tch ln,
nhng phng phap nay co th xay ra nguy c "qua bao v". Ngha la, in th
in cc cuc b cua cng trnh tr nn qua m n ni tc cua phan ng:

+ + OH H e O H 2 2 2
2 2
tr nn ang k.
Cac phng phap bao v trn thng c dung kt hp vi cac lp phu
cach in, nn vung tac dung bao v cua protector tng ln rt nhiu.




















CHUO^G 6
NHUNG NHN T ANH HUONG DN TC D N MON

I/ Nhung nhn t bn trong:
1.1. Tinh bn nhit dng cua kim loai:
in th in cc tiu chun co th anh ga gn ung tnh bn nhit ng
cua kim loai. Tc n mon cung co th tnh theo cng thc nh sau:

R
E E
I
cb
a
cb
c

=
I phu thuc vao va , tc phu thuc vao ban cht cua kim loai.
cb
c
E
cb
a
E
V du: - Trong mi trng trung tnh nhng kim loai nao co
in th in cc m hn se b hoa tan: Na, K, Zn, Al, Fe ...Nhng kim loai nao co
in th dng hn khng th hoa tan: Cu, Ag, Au, Hg, ...
V E
cb
H
41 . 0
2
=
- Trong mi trng axit nhng kim loai nao co in th in
cc m hn se b hoa tan: Zn, Al, Fe, Pb ...Nhng kim loai nao co in th dng
hn khng th hoa tan: Cu, Ag, Au, Hg, ... nhng khi trong dung dch co oxy hoa
tan th Cu, Hg, Ag lai b n mon do s kh phn cc oxy.
0
2

cb
H
E
2.2. Vj tri cua kim loai trong bang h thng tun hoan:
Khng phan anh ro net tnh bn chung cua kim loai v no con phu thuc vao
tnh cht bn trong va bn ngoai na. No ch phan anh mt s tnh cht co tnh qui
lut ma thi.
V du: - bn nhit ng cua kim loai tng t trn xung i vi cac
nhom IB, IIB, VIIIB.
- Nhng kim loai d b thu ng la nhng kim loai thuc nhom IVB,
VIB, VIIIB.
II/ Nhung nhn t bn ngoai:
2.1. Anh huong cua pH:
a/Anh huong truc tip: o la anh hng do cac phan ng kh phn
cc hydro va oxy. Khi thay i pH mt gia tr n v th in th se thay i
0.059V.
b/ Anh huong gian tip: thay i pH co th hoa tan san phm n
mon hay tao thanh mang bao v trn b mt in cc.
Ngi ta chia thanh 3 nhom (Hnh 6.1)


K K K







1 pH 2 pH 3 pH
Hnh 6.1.
* Nhng kim loai ma mang oxyt cua no hoa tan trong axit va trong kim:
Al, Zn, Sn, Pb. Trong mi trng axit no tao thanh cac ion kim loai Al
3+
, Zn
2+
,
Sn
2+
, Sn
4+
, ...Trong mi trng kim tao thanh phc cht ZnO
2
2-
, AlO
2
-
, ...(dang 1).
* Nhng kim loai ma mang oxyt cua no hoa tan trong axit ma khng b hoa
tan trong kim (do tao thanh cac oxyt kho tan): Ni, Co, Cu, Cr, Mn, Fe (dang 2).
* Nhng kim loai ma mang oxyt cua no khng hoa tan trong axit va trong
kim. Tc n mon khng phu thuc vao pH: Pt, Au, Ti, ... (dang 3).
i vi mi kim loai pH khac nhau co tc n mon khac nhau.
Bang 6.1.
Kim loai Al Pb Sn Zn Fe
pH co tc n mon cc tiu 6.6 8 8.5 11.5 14

2.2. Anh huong cua thanh phn va nng d cua dung djch mui:
Tc n mon in hoa phu thuc vao ban cht cua dung dch mui hoa
tan va nng cua no trong dung dch.
- Mui co tnh oxy hoa lam chm tc n mon, co khi ngn can hoan toan
qua trnh n mon do kim loai b thu ng: KClO
3
, K
2
CrO
4
, KNO
2
, ...Ngc lai nu
mui co tnh oxy hoa la cht kh phn cc th se lam tng tc n mon: S
2
O
8
2-
,...
- Nhng mui co tnh axit hay baz khi tng nng cua no th pH tng
nn co anh hng nh pH: Na
2
CO
3
, AlCl
3
, ...Tuy nhin, cung co nhng loai mui
axit khi tac dung vi kim loai tao thanh mui khng tan trn anod hay catod se lam
giam tc n mon: MeH
2
PO
4
, Me(HPO
4
)
2
, ...
- Tc n mon con phu thuc vao ban cht, nng cua cation va anion
cua mui hoa tan. Nu cac anion cua mui co kha nng hp phu trn b mt kim
loai lam thay i c cu lp in tch kep, lam giam in th in cc cua kim loai
lam cho tc n mon giam. Nhng nu anion co hoat tnh ln se pha v mang
thu ng nn tc n mon tng.
K(mm/nm) K(mm/nm)
KF

KCl KCl
NaCl
KBr
KI LiCl


t.gian nng
Hnh 6.2. Tc n mon phu thuc vao Hnh 6.3. Tc n mon phu thuc
Dang anion co trong dung dch vao dang cation va nng cua mui

2.3. Anh huong cua nng d oxy:
n mon kim loai trong a s cac trng hp do s kh phn cc cua oxy,
cho nn tc n mon phu thuc vao tc hoa tan cua oxy.
K






6 12 18 24 cm
3
/l
Hnh 6.4.
2.4. Anh huong cua nhit d:
Nhit anh hng ln n tc n mon. Trong dung dch in li tc
n mon tng khi tng nhit .






K





Hnh 6.5. T
2.5. Anh huong cua tc d chuyn dng dung djch:
Trong cng nghip hoa cht co rt nhiu thit b lam vic trong mi trng
cht in giai chuyn ng nh bm, van, ng ng, thap hp thu, hp phu, canh
khuy,... trong mi trng nay tc n mon co th tng hay giam.
- Nu cht long khng cha anion hoat ng: F
-
, Cl
-
, Br
-
, I
-
th ban u tng
tc chuyn ng cua cht long th tc n mon tng, nhng sau o giam. Nu
tng manh tc chuyn ng cua dong cht long th tc n mon tng.
- Nu trong cht in giai co cha cac anion hoat ng th khng th nao
tao mang thu ng. Do o, tc n mon tip tuc tng.
K K







m/s m/s
Hnh 6.6.
2.6. Anh huong cua dong din ro:
Rt nhiu thit b va ng ng lam vic ngm di at b n mon do tac
ng cua dong in ro (chu yu la dong mt chiu, dong xoay chiu khng anh
hng)







(+)



(-)



vung catod vung trung hoa vung anod (n mon manh)
Hnh 6.7.
2.7. Anh huong cua cac nhn t khac:
Do mt vai khu trong chi tit khng ung qui cach, gy nn n mon. Nguy
him nht la cac ch ni, ch han, cac mi han. (Hinh 6.8.)









Tranh bt mai mon D gy mai mon
Hnh 6.8.
III/ Cht lam chm n mon: (CLC)
3.1. Khai nim:
Cht lam chm n mon la cht khi thm vao mi trng mt lng nho th
tc n mon in hoa cua kim loai va hp kim giam i rt ln. C cu tac dung
cua cht lam chm la ngn can qua trnh anod va catod hay tao mang.
Theo Balezin cht lam chm co th chia lam cac loai sau:
Kiu A: Cht lam chm tao trn b mt hp kim mt lp mang mong.
Kiu B: Cht lam chm lam giam s xm thc cua mi trng.
Kiu AB: kt hp hai loai trn.
Ngoai ra theo mt s tac gia khac cht lam chm gm co cac loai sau:
Da vao thanh phn: CLC v c, CLC hu c.
Da vao tnh cht s dung: CLC trong dung dch, CLC bay hi.
Da vao tnh cht mi trng: CLC axit, CLC kim, CLC trung tnh.
danh gia CLC da vao hai ch s sau:
H s tac dung bao v (Z):
(%)
0
1 0
K
K K
Z

=
K
o
: Tc n mon kim loai trong dung dch cha co CLC (g/m
2
.h).
K
1
: Tc n mon kim loai trong dung dch khi co CLC (g/m
2
.h).
Hiu qua bao v ():
(%)
0
0
K
K
=
2.2. Cht lam chm anod:
Thng la nhng cht oxy hoa, nhng cht nay ngn can qua trnh anod, no
lam thu ng hoa b mt anod va lam giam qua trnh anod. Nhng CLC anod
thng c s dung: Na
2
CrO
4
, NaNO
2
, hn hp cua (NaNO
2
+ NaCO
3
), ...
V du: Cromat hoa b mt st, thep:

O O O O O O O O
Cr Cr Cr Cr Cr Cr Cr
O O O O O O O O

Fe Fe Fe Fe
Hnh 6.9.
3.3. Cht lam chm catod:
Thng la nhng cht hp thu oxy, do o lam giam tc n mon do s
kh phn cc oxy. Ngoai ra nhng cht nay lam giam hiu ng cua catod hay giam
b mt catod. Nhng CLC catod thng c s dung: Na
2
SO
3
, Ca(HCO
3
)
2
, NH
2
-
NH
2
, ZnSO
4
, ... Ngoai ra, cung co mt s ion kim loai nh As
3+
, Bi
3+
trong mi
trng axit chung se phong in trn catod tao thanh As hay Bi. Qua th hydro
trn cac kim loai nay cao hn qua th hydro trn thep.
3.4. Cht lam chm huu co:
Ngay nay, ngi ta a tm ra trn 3000 CLC, trong o a s la CLC hu c.
Tac dung cua CLC hu c la hp phu ln b mt kim loai va lam giam tc n
mon.
Anh hng cht hp phu n tc n mon do hai nhn t chnh:
+ Mc bao phu b mt bi ion hay phn t cua CLC hu c.
+ Thay i in th khi b hp phu.
Mt s CLC hu c thng c s dung trong mi trng axit H
2
SO
4
22%
nh sau:
Bang 6.2.
Tn cht Cng thc Nng Z(%) (%)
Utrotropin (CH
2
)
6
N
4
11.2% 96.798 3147
Thioure' (NH
2
)
2
CS 0.0050.01% 96 2425
Pyridin C
5
H
5
N 1.52% 40 1.7
Kaliiodua KI 0.11% 65 98.5
Benzidin NH
2
C
5
H
6
9g/l 87.7 96.5


3.5. Cht lam chm bay hoi:
Cht lam chm bay hi dung bao v kim loai khi tip kim loai o tip
xuc vi khoi hoc hi, nn c goi la CLC bay hi. CLC bay hi co ap sut hi
bao hoa cao, hi cua no nhanh chong chim y th tch khng gian kn, sau o
c hp thu ln b mt kim loai va bao v kim loai trong mt thi gian dai.
Nhung dc trung quan trong cua CLC bay hoi la:
+ P
hbh
= 10
-2
10
-4
mmHg 2025
o
C.
+ Co tac dung bao v kim loai lam vic trong khng gian kn.
Tac dung cua CLC bay hoi:
Cht lam chm bay hi co th tac dung vi cac cht kh phn cc, lam
giam m cua mi trng, lam cho b mt kim loai ghet nc, hay co th tao
mang thu ng.
Phuong phap su dung CLC bay hoi:
+ Cho CLC bay hi trong khng gian kn: phong, hom kn.
+ Quet CLC bay hi trn giy bao goi.
Mt s CLC bay hoi thuong duoc su dung:
+ CLC phtphat, loai nay thng c dung bao v thep, gang, crom,
niken, thic. Phi liu nh sau:
77% NaNO
2
+ 5.5% (NH
4
)
2
HPO
4
+ 1% Na
2
CO
3
(trong lng)
Hn hp nay dang bt, cho vao bao b va c 1m
3
khng gian cn 1.5kg
bt.
+ CLC bay hi trn c s natrinitrit va benzoat.
32.5% Benzoat + 16.5% NaNO
2
+ 1% (NH
4
)
2
CO
3
(trong lng)
3.6. Cht lam chm hoa tan trong du mo:
Cht lam chm hoa tan trong du m la hp cht hu c ma phn t cua no
co cu tao t hai phn:
+ Gc hydrocacbon co phn t cao (thng hay vong)
+ Nhom hoat ng bao v kim loai
Cng thc chung: C
n
H
2n+1
A.
A: -OH, -COOH, -COOMe, -SO
3
, --SO
3
Me, -NO
2
, -NH
2
.
Co cu tac dung cua CLC trong du mo:
+ Ngn can s khuych tan cua nc va kh n mon qua du m.
+ Tao trn b mt in cc mang hp thu ghet nc, khng cho nc i qua,
khng b nc phn huy.
Mt s cht CLC trong du mo hin nay duoc su dung:
Nitro hoa m khoang (co gn gc -NO
2
), hp cht hydrocacbon mach cao
co gn cac gc -SO
3
, -NO
2
, -NH
2
, hoc hn hp mt s m co nhiu gc hoat ng
th hiu qua bao v cao hn so vi n cht.

























CHUO^G 7
LOP PHU BAO V

Lp phu bao v la mt trong nhng phng phap ph bin nht hin nay chng
n mon kim loai.
Co ba loai lp phu bao v:
Lp phu kim loai
Lp phu phi kim loai
Lp phu bng cac hp cht hoa hoc.
A. Lop phu kim loai:
I. Co cu:
1.1. Lop phu anod:
in th kim loai phu m hn kim loai chnh, do o kim loai phu ong vai tro
anod cua pin n mon. V du : Zn, Sn, Cd, ... ln trn nn st, thep.
1.2. Lop phu catod:
in th kim loai phu dng hn kim loai chnh, do o kim loai phu ong vai tro
catod va kim loai chnh ong vai tro la anod. Do o, mun bao v kim loai chnh
lp phu phai am bao cac yu cu:
- Bn trong mi trng n mon.
- St chc, khng co l xp, khng co vt nt.
- Bam chc vao kim loai chnh.
V du: Cu, Cr, Ni ln trn nn st, thep.
II. Phuong phap phu:
2.1. Phuong phap din: s dung ngun in mt chiu
Ban cht cua phng phap nay la kt tua in hoa t cac kim loai khac.

+ -
R
A
Zn Fe








Hnh 7.1.
2.2. Phuong phap nhit:
Ban cht cua phng phap nay la nhung kim loai cn bao v vao kim loai khac
dang nong chay va kim loai nong chay bam ln b mt kim loai cn bao v.
Nhng yu cu c ban tao thanh lp phu:
- Kim loai nong chay co kha nng thm t va dang u trn b mt kim loai cn
bao v.
- Tao thanh hp kim gia hai kim loai.
- Nhit nong chay thp hn kim loai cn bao v.
* Uu dim: n gian, nng sut cao.
* ^huoc dim:
+ Chiu day lp phu khng n nh, phu thuc vao nhit va thi gian nhung.
+ Tiu hao kim loai kha ln (lam vic nhit cao nn kim loai d b oxy hoa)
+ Lp phu khng u, khng bng phng
+ Khng th thc hin c vi cac chi tit phc tap (l, khe)
2.1.1. Nhung kem:
Zn co in th m hn Fe nn co th bao v st khoi n mon trong khng kh va
trong nc.
a. Cac buoc tin hanh:
- Ty du m trong dung dch 6-10% NaOH, 2-5% Na
3
PO
4
80
o
C.
- Ty g hoa hoc trong dung dch 5-10% H
2
SO
4
thi gian 30-35' (co the ty g in
hoa)
- Hoat ng hoa b mt Fe trong dung dch 0.5-3% HCl hay trong dung dch
NH
4
Cl a acid hoa.
- Tr dung hoa b mt kim loai.
- Sy nhit 120-200
o
C.
- Nhung vao dung dch Zn nong chay.
b. Vai tro cua cht tro dung:
Muc ch cua cng oan nay la lam sach cac cht bn trn b mt kim loai
tranh cho kim loai khoi b oxy hoa va lam cho kim loai thm t tt vi kim loai
nong chay.
Cht tr dung chia lam hai loai:
* 1ro dung uot: 42-43% NH
4
Cl + 13-14% ZnO + 42-43% ZnCl
2
.
Cht tr dung nong chay trn kim loai nong chay.
Cac phan ng co th xay ra nh sau:
- Khi cht tr dung tac dung vi Zn nong chay:
Zn + 2NH
4
Cl Zn(NH
3
)
2
Cl
2

Zn(NH
3
)
2
Cl
2
ZnNH
3
Cl
2
+ NH
3

- Oxyt st b kh theo phan ng:
FeO + NH
4
Cl FeOHCl + NH
3

FeOHCl + ZnNH
3
Cl
2
FeCl
2
+ ZnOHCl + NH
3

ZnOCl ong vai tro chnh trong vic thm t b mt Fe. Vi vy, ZnCl
2
co vai tro
quan trong trong cht tr dung v:
ZnCl
2
+ H
2
O [Zn(OH)
2
Cl
2
]H
2
- Ngoai ra co cac phan ng sau:
FeCl
2
+ Zn ZnCl
2
+ Fe
ZnO + 2NH
4
Cl ZnCl
2
+ 2NH
3
+ H
2
O
* 1ro dungkh: 50% ZnCl
2
c hoa tan trong thit b ring, trc khi nhung Zn,
cho kim loai Fe nhung vao ZnCl
2
, sau o sy kh, nhung vao Zn nong chay.
2.1.2. Cu tao cua lop Zn:
Nhung Fe vao Zn nong chay tao thanh lp phu Zn. Lp phu nay co nhiu lp, qua
nghin cu cu tao cua no co th chia lam 6 lp:
- Lop : la lp dung dich rn chua khoang 95% trong lng Fe.
- Lop : co dang Fe
5
Zn
21
hay Fe
3
Zn
10
cha khoang 18-20% trong lng Fe.
- Lop : co dang FeZn
7
cha 7-12% trong lng Fe.
- Lop : co dang FeZn13 cha 6% trong lng Fe.
- Lop : ham lng Zn kha nhiu, ham lng Fe ch con 0.003%.
- Lop : la lp trung gian gia lp va lp . Lp nay don lam giam bn cua
lp phu.
Lp +: chiu day cua lp Zn chim 50-60% chiu day cua lp phu.
2.1.3. Anh huong cua nhit d va tap cht:
* Anh huong cua nhit d: nhit cang cao lp phu cang mong, chiu day cua
lp cang nho, nn Zn b oxy hoa cang cao gy tn tht ln. Ngc lai, nhit
cang thp chiu day lp phu cang ln, nhng lp phu t bng phng va kho thao
tac.
Thng thng khng ch nhit khoang 435-470
o
C.
* Anh huong cua tap cht: Al la nguyn t kha quan trong, nu trong Zn
nong chay co khoang 0.2-0.4% Al th du phng phap tr dung t hay kh u
cho lp Zn bong. Nhng nu ham lng Al nhiu hn se lam thay i tnh cht c
hoc cua lp phu.
Tng ham lng Al th chiu day cua lp se giam, lam cho chiu day chung
giam. Khi ham lng Al at n mt gii han nao o th lp trung gian bin mt
va nu ham lng Al vt qua 0.4% th AlCl
3
c tao thanh va lam can tr phan
ng gia Fe va Zn. Ngoai ra, cac tap cht khac nh: Pb, Cd, Bi cung anh hng
n chiu day cua lp phu Zn.
2.1.4. Cu tao cua thung nhung Zn:




1 2

3 4



5
Hnh 7.2.
1. Lp Zn nong chay; 2. Cht tr dung nong chay; 3. Lp Pb nong chay
4. Vt trang; 5. Vo thung (bng thep co lot lp gach samt)
2.2. Nhung thic: (oc tai liu)
B. Lop phu phi kim loai:
Co hai loai ph bin hn ca la sn va trang men.
I. Trang men:
Dung bao phu cac thit b phan ng co vo boc gia nhit, thap hp thu, ng trao
i nhit (rut ga), ...
1.1. Co cu bao v cua lop men:
Lp men bam chc vao kim loai, hoan toan khng co l xp. Nc va khng kh
khng th thm qua c. bn cua kim loai chnh la bn cua lp men. Kim
loai c trang men co nhng u, nhc im nh sau:
* Uu dim:
- Lp men tng i bn trong mi trng xm thc: kh quyn, dung dich mui
trung tnh, trong nc, trong acid co tnh oxy hoa, kim yu.
- Gi ve ep va n nh trong mt thi gian dai.
- Cng ngh trang men n gian, nguyn liu d tm.
* ^huoc dim:
- Khng the boc lp phu ra c, do o khi lp men h th khng th phuc hi chi
tit nh ban u c.
- Lp men d v do tac dung c hoc.
- Khng th thc hin c cho cac chi tit phc tap.
- trong mi trng kim manh, hoc mi trng HF lp men se b pha huy:
SiO
2
+ 2NaOH Na
2
SiO
3
+ H
2
O
SiO
2
+ HF SiF
4
+ 2H
2
O
1.2. Nguyn liu san xut men: co 2 nhom chnh
* Jt liu tao thanh thuy tinh: cat thach anh la vt liu chnh san xut ra men.
Thanh phn SiO
2
chim t 95-98.8%, nhit nong chay cao 1600-1700
o
C, cho
nn cn phai thm mt s cht phu gia.
* Cac cht phu gia: tuy thuc vao tnh cht cua men ma cho cac cht phu gia khac
nhau:
- Ha thp nhit nong chay dung Na
2
O.PbO
- Men bn hoa thm cac loai oxyt B
2
O
3
.PbO
- Anh hng h s gian n nhit thm Na
2
O.K
2
O
- Cht lam uc CaF
2
, 3NaF.AlF
3
(criolit Na
2
AlF
6
)
- Cht oxy hoa oxy hoa cacbon dang bn: NaNO
3
, KNO
3
, MnO
2
.
- Cht tao mau:
Pb
2
Pb
4
O
7
: mau vang
C
o
O + Cr
2
O
3
: mau xanh nc bin
Cr
2
O
3
: mau xanh la cy
1.3. Trang men:
* Men nn: phai am bao men bam chc vao kim loai, khng cho kim loai tac
dung vi mi trng xm thc. Chiu day cua lp men nay 0.1-0.2 mm.
* Men ngoai: trang tr va bn c hoc.
Trang men co th dung hai phng phap t hay kh.
II. Son:
Sn la loai cht long c cu tao t cht tao mang va mt s cht hoa tan trong
dung mi d bay hi. Tuy thuc vao cht tao mang ma co nhiu loai sn khac
nhau.
2.1. Vai tro cua lop son:
- Chng g
- Trang tr
- Cach in, sn chu nhit, chu ha, chu acid, chu kim, chu xng du.
2.2. Yu cu cua mang son:
- Sn phai bam chc vao kim loai nn.
- Phai n nh hoa hoc
- Khng thm nc, thm kh, khng b nc phn huy.
- Phai chm lao hoa.
2.3. Thanh phn mang son:
Cht tao mang: la thanh chu yu, cht tao mang co th la: du thao mc, nha
thin nhin, nha tng hp.
* Dung mi: cht long d bay hi, dung hoa tan cht tao mang.
* Bt mau: cac oxyt kim loai mn hoc cac bt mau hu c, khng hoa tan trong
nc, co tac dung lam cho mang sn nhn, co mau ep, co bn c hoc cao.
Lng bt mau chim khoang 10% trong lng sn.
2.4. qua trinh gia cng mang son:
- X l b mt trc khi sn
- Chon sn
- Cac lp sn
+ Sn nn: lam cho b mt khng g va lam nn
+ Sn lot: lam phng b mt lp sn nn
+ Sn phu: tuy theo yu cu va tac dung ma chon sn.
- Sy kh mang sn.
C. Lop phu hop cht hoa hoc:
I. Oxy hoa va nhum mau kim loai:
1.1. Oxy hoa kim loai den:
bao v kim loai en khoi n mon thng ngi ta tao trn b mt kim
loai o mt lp oxyt theo phng phap hoa hoc hay in hoa. Phng phap in
hoa t c s dung va khng c cp trong phn nay.
a. Oxy hoa theo phuong phap hoa hoc:
Qua trnh nay thng c tin hanh trong dung dch kim c co cha cac cht
oxy hoa.
Phng phap hoa hoc c dung ph bin hn phng phap in hoa.
C cu tao mang oxyt nh sau:
- Hoa tan Fe trong kim tao thanh mang oxyt (mui oxyt thp):
Fe Na
2
FeO
2

- Oxy hoa mui oxyt thp thanh mui oxyt cao:
Na
2
FeO
2
Na
2
Fe
2
O
4

- Tac dung hai mui trn tao oxyt st t:
Na
2
FeO
2
+ Na
2
Fe
2
O
4
Fe
3
O
4

- Thuy phn mui oxyt cao:
Na
2
Fe
2
O
4
+ (m+1)H
2
O Fe
2
O
3
.mH
2
O
- Kh hydrat hoa mt phn:
Fe
2
O
3
.mH
2
O Fe
2
O
3
.(m -1)H
2
O
Cac giai oan trn co th c tng quat nh sau:
Fe Na
2
FeO
2
Na
2
Fe
2
O
4
Fe
2
O
3
.mH
2
O Fe
2
O
3
.(m -1)H
2
O

Fe
3
O
4

(mang oxyt) (bun mau o kt tua trn ay thung)
Cu tao mang va chiu day mang phu thuc vao tc tao thanh trung tm
kt tinh va tc phat trin mang. Nu tc tao trung tm kt tinh ln hn tc
phat trin mang (nng cht oxy hoa cao) th mang tao thanh nhanh, st chc,
nhng mong. Ngc lai, Nu tc tao trung tm kt tinh be hn tc phat trin
mang (nng kim cao) th mang tao thanh day nhng xp.
Cht oxy hoa c s dung y la cac mui nitric va nitrat. Dung mui
nitric cho mau xanh sang, con mui nitrat cho mau en.

Bang 7.1. Thanh phn va ch oxy hoa
STT Thanh phn Ch oxy hoa

1
NaOH
NaNO
3

NaNO
2

700-800 g/l
200-250 g/l
50-70 g/l
138-140
o
C
(khi nhung)
142-146
o
C
(khi ly ra)

20-120 phut


2
NaOH
NaNO
3

1000-1100 g/l
130-140 g/l

145-150
o
C
(khi nhung)
160-165
o
C
(khi ly ra)

60-90 phut


Dung dch 1 cho mang oxyt bong, dung dch 2 cho mang oxut m.
Ngoai ra co th tin hanh oxy hoa kim loai en trong dung dch acid H
3
PO
4
th cho
mang oxyt tt hn v ca tnh cht c hoc va bn lin kt, bn n mon so vi
dung dch kim. c bit, qua trnh nay co th tin hanh oxy hoa cho ca kim loai
en va kim loai mau. Qua trnh tin hanh nhanh, t tn nhit lng.
Bang 7.2. Thanh phn va ch oxy hoa
Cu tu
Thanh phn (g/l) Nhit Thi gian
H
3
PO
4

Ca(NO
3
)
2
.4H
2
O
Ba(NO
3
)
2

MnO
2

Ni
Fe(H
2
PO
4
)
2

Mn(H
2
PO
4
)
2

4-10
70-100
-
1.0-2.0
-
-
4-10
-
70-100
1.0-2.0
8-10
-
2-10
-
70-100
1.0-2.0
-
30-40



100
o
C


40-45 phut

1.2. Oxy hoa kim loai mau:
bao v va trang tr kim loai mau, ngi ta thng tao trn b mt kim loai o
mt lp oxyt theo phng phap hoa hoc hay in hoa.
1.2.1. Oxy hoa dng:
Oxy hoa ng chng n mon, trang tr trong cng nghip va thit b quang hoc.
a. Oxy hoa theo phuong phap hoa hoc:
Mang oxyt tao thanh day khoang 1m, co thanh phn chu yu la CuO.
Thanh phn va ch oxy hoa nh sau:
NaOH 50 g/l
K
2
S
2
O
8
15 g/l
Nhit 60-65
o
C
Thi gian 5 phut
b. Oxy hoa theo phuong phap din hoa:
Mang oxyt tao thanh day khoang 1-2m, co bn c hoc va bn n mon cao
va co th oxy hoa cac loai hp kim cua Cu.
Thanh phn va ch oxy hoa nh sau:
NaOH 100-250 g/l
Nhit 80-90
o
C (Cu)
60-70
o
C (ng thau)
i
a
0.5 A/dm
2

in th 2-6 Volt
Thi gian 30 phut
oxy hoa va nhum mau vang cua ng, ngi ta khng s dung dong
in ngoai ma ch cho Cu tip xuc vi Al. Gia Cu va Al se xut hin mt hiu
in th.
Thanh phn va ch oxy hoa:
CuSO
4
50 g/l
NaOH 35 g/l
C
2
H
2
O
4
30 g/l
pH 9.2-9.6
Nhit 20-32
o
C
Thi gian 7 phut
T l b mt Cu:Al = 4:1
Dung dch khac nhau cho mau khac nhau va thi gian khac nhau cung cho
mau khac nhau.
1.2.2. Oxy hoa nhm:
a. Oxy hoa theo phuong phap hoa hoc:
Oxy hoa Al theo phng phap nay, chiu day mang oxyt Al at c khng
cao khoang 0.5 - 1m va co bn kem.
Thanh phn va ch oxy hoa:
Na
2
CO
3
50 g/l
NaOH 2-2.5 g/l
Na
2
CrO
4
15 g/l
Nhit 80-100
o
C
Thi gian 5-30 phut
b. Oxy hoa theo phuong phap din hoa:
- Co cu tao mang oxyt:
Qua trinh anod:
Al Al
3+
+ 3e (1)
OH
-
O
2
+ H
2
O + 4e (2)
Qua trnh nay co th chia lam nhiu giai oan:
2OH
-
O
2-
+ H
2
O
O
2-
O
-
+ e
O
-
O + e
2O O
2
2Al
3+
+ 3O
2-
Al
2
O
3
(3)
2Al + 3O Al
2
O
3
(4)
Qua trinh catt:
H
+
+ 2e H
2
(5)
Nhm khi mi cho vao dung dch in li co th xay ra phan ng sau:
2Al + 3H
2
SO
4
Al
2
(SO
4
)
3
+ 3H
2
(6)

Mang c hnh thanh se tac dung vi dung dch in li:
Al
2
O
3
+ 3H
2
SO
4
Al
2
(SO
4
)
3
+ 3H
2
O (7)
- Co cu phat trin mang oxyt va hinh thanh cac l xp:
Qua trnh tao mang oxyt xay ra theo phan ng (3) va (4). Lp oxyt nhm
mi hnh thanh mong st va chiu day hu nh khng thay i. Khi a tao mang
oxyt th cung tn tai hai qua trnh la phat trin mang va hoa tan mang (phan ng
7). Qua trnh hoa tan nay lai trn b mt lp oxyt nhm nhiu l xp, luc nay
oxy nguyn t va ion oxy khuych tan qua mang di ay cac l xp o tip tuc
oxy hoa nhm. Lp oxyt mi lai c hnh thanh, lp nay nm gia b mt phn
chia kim loai va oxyt, phn nay se phat trin v moi hng la lam cho lp oxyt day
thm. Mt khac, trn day l xp pha ngoai mang se xay ra qua trnh hoa tan mang
oxyt. Hai qua trnh xay ra ng thi va canh tranh nhau. Nu tc phat trin
mang ln hn tc hoa tan mang th lp oxyt day se c tao thanh. Ngc lai,
tc phat trin mang nho hn hoc bng tc hoa tan mang th lp oxyt se
khng c tao thanh hoc b hoa tan.
Tom lai, lp oxyt bao gm hai lp: lp trong cung mong st, lp ngoai day
co nhiu l xp (chnh l xp la cac trung tm phat trin mang).
Ngoai ra, trn thanh cac l xp ngoai cung co ca phan ng hydrat:
Al
2
O
3
+ H
2
O Al
2
O
3
.H
2
O (8)
Hay Al
2
O
3
+ 3H
2
O Al
2
O
3
.3H
2
O (9)
Va cung co qua trnh hoa tan:
Al
2
O
3
.nH
2
O + 3H
2
SO
4
Al
2
(SO
4
)
3
+ (n+3)H
2
O (10)
Chu y:
- S phat trin mang oxyt phu thuc vao t l tc cua hai qua trnh din
bin ng thi: s hnh thanh mang nh oxy hoa in hoa va hoa tan mang do tac
dung cua cht in li.
- Tc tao mang c xac nh bng mt dong (i
a
cao tao mang
nhanh). Tc hoa tan mang phu thuc vao ban cht va nhit cua dung dch
in li (nhit cao, tc hoa tan mang ln).
- 1hanh phn va ch d oxy hoa:
Co th s dung nhiu loai cht in li khac nhau tuy thuc vao muc ch s
dung mang oxyt, nhng thng thng ngi ta hay s dung dung dch H
2
SO
4
lam
cht in li.
Dong in s dung co th la dong xoay chiu hay mt chiu, nhng dung
dong mt chiu cho mang oxyt cng, st hn.

Bang 7.3. Thanh phn va ch oxy hoa
Thanh phn va ch Dong mt chiu Dong xoay chiu
H
2
SO
4
(g/l)
Nhit (
o
C)
i
a
(A/dm
2
) Al
i
a
(A/dm
2
) Dura
in th (Volt) Al
in th (Volt) Dura
Thi gian (phut)
180-200
15-23
1.5-2
0.8-1.2
12-13
13-28
40-50
125-130
12-25
1.5-2
1.5-2
21-28
19-26
40-50 (Al)
30-40 (Dura)
Chu y: mun co mang oxyt day, chu mai mon phai oxy hoa trong dung dch lanh
13
o
C, i
a
=22.3 A/dm
2
, thi gian = 34 h.
1.2.3. Nhum mau nhm va hop kim nhm:
Do mang oxyt co nhiu l xp nn co kha nng hp phu cac cht mau hu
c, v c, di khi cac cht mau nay tac dung vi mang oxyt tao thanh cac hp cht
hoa hoc. Ngoai ra, cac phan ng tao mau co th xay ra trn l xp lam cho mang
oxyt co mau.
V du: mun nhum mau vang da cam cho nhm, ngi ta nhung mu
nhm a ant hoa vao dung dch 510g/l K
2
Cr
2
O
4
thi gian khoang 30 phut, ra
sach, sau o em nhung vao trong dung dch 50100g/l AgNO
3
cung trong thi
gian 30 phut. Mau cua mang oxyt se xut hin do phan ng sau
K
2
Cr
2
O
4
+ AgNO
3
= Ag
2
Cr
2
O
4
+ 2KNO
3

vang da cam
Bang 7.4. Thanh phn dung dch khi nhum mau cac hp cht v c.
Dung dch 1 Dung dch 2 Mau
nhum
Mui
Nng
(g/l)
Mui Nng
(g/l)
Hp cht
mau
Xanh FeCl
2
10-100 K
4
Fe(CN)
6
10-50 Xanh da tri
Da lng CuSO
4
10-100 K
4
Fe(CN)
6
10-50 CuFe(CN)
6

Vang Pb(CH
3
COO)
2
100-200 K
2
Cr
2
O
7
50-100 PbCr
2
O
7

Trng Pb(CH
3
COO)
2
10-50 Na
2
SO
4
10-50 PbSO
4

Vang anh Na
2
SO
3
10-50 KMnO
4
10-50 MnO
en Co(CH
3
COO)
2
10-100 KMnO
4
15-25 CoO


Bang 7.5. Thanh phn dung dch khi nhum mau cac hp cht hu c.
Tn cht mau Nng (g/l) pH Nhit (
o
C)
Alizarin vang 5 50
Vang da cam cho nhm 1-3 4-5 20-25
Mau tm cho nhm 1 4-7 50-60
Vang 53 cho nhm 1 6-7 50-60
Xanh cho nhm 1 3-4 50-60
Alizarin o 2 50-60

1.2.4. So d mach:


+ -






H
2
SO
4

Pb
Pb
R A
Al


Hnh 7.3.
II. Pht phat hoa kim loai:
La tao trn b mt kim loai mang pht phat khng tan bam chc vi kim
loai nn. Mang pht phat khng chu c trong dung dch axit va kim manh.
nhit cao (400-500
o
C) mang pht phat cung khng chu c lu.
2.1. Pht phat hoa nong:
2.1.1. Pht phat hoa thuong:
Nhung mu thep vao dung dch mui pht phat dang hoa tan, thng s
dung la mui Majef: Mn(H
2
PO
4
)
2
.H
2
O, Mn(HPO
4
), Fe(H
2
PO
4
)
2
hay monophotphat
Zn. Co dang tng quat nh sau: Me(H
2
PO
4
)
2

Mui nay nhit thng b phn huy nhng khng ang k:

4 3 4 2 4 2
) ( ) ( PO H HPO Me PO H Me + (1)
un nong se phn huy trit hn:
4
4 3 2 4 3 4 2 4 2
5 ) ( ) ( ) ( PO H PO Me HPO Me PO H Me + + (2)
Khi nhung thep vao dung dch pht phat se xay ra hai qua trnh sau:
* Qua trnh ant:
+

2
Fe Fe
* Qua trnh catt:
2
2 2 H e H +
+
Ion H
+
do s phn li cua H
3
PO
4
t do hay do cac phan ng sau:
(3)
+
+
4 2
2
2 4 2
2 ) ( PO H Me PO H Me
(4)
+
+
2
4 4 2
HPO H PO H
(5)
+
+
3
4
2
4
PO H HPO
Kt qua la lp dung dch gn sat b mt mu thep giau ion Fe
2+
cung nh
cac ion HPO
4
-
va PO
4
3-
. Tch s tan cua FeHPO
4
, MnHPO
4
, cung nh Fe
3
(PO
4
)
2
,
Mn
3
(PO
4
)
2
rt nho. Do vy, lp dung dch gn sat b mt mu thep at n qua bao
hoa va kt tinh ln b mt thep tao thanh lp phu pht phat theo phan ng:
(6)
4
2
4
2
FeHPO HPO Fe = +
+
Mn (7)
4
2
4
2
MnHPO HPO = +
+
(8)
4
2
4
2
ZnHPO HPO Zn = +
+
3 (9)
2 4 3
3
4
2
) ( 2 PO Fe PO Fe = +
+
3 (10)
2 4 3
3
4
2
) ( 2 PO Mn PO Mn = +
+
3 (11)
2 4 3
3
4
2
) ( 2 PO Zn PO Zn = +
+
Thi gian pht phat hoa khoang 35-50 phut, nhit dung dch duy tr
khoang 96-98
o
C. Nhit cao, mui se b phn huy theo phan ng (1) va (2). Do
o, MeHPO
4
va Me
3
(PO
4
)
2
co th kt tua ln b mt thep va ca ngoai dung dch.
Ngc lai, nu nhit thp th thi gian pht phat hoa se keo dai.
Thi gian, chiu day, cu truc cua lp pht phat hoa phu thuc vao cac yu
t sau:
- Kim loai.
- Phng phap gia cng b mt trc khi pht phat hoa.
- Nhit .
- Tap cht co trong dung dch (SO
4
2-
, Cl
-
)
- T s axit chung va axit t do.
D axit tu do c xac nh bng phep chun vi metyldacam. C
10ml dung dch th mt 3-4ml NaOH 0.1N
D axit chung c xac nh bng phep chun vi phenolphtalein.
C 10ml dung dch th mt 28-30ml NaOH 0.1N
Lng dung dch NaOH 0.1N chun nay c biu th bng im. V vy,
ch s axit chung 28-30 im va ch s axit t do 3-4 im.
1hanh phn va ch d lam vic:

Majef 32g/l
Nhit 98-100
o
C
Thi gian 40-65 phut
Axit chung/Axit t do 7-8
2.1.2. Pht phat hoa nhanh:
giam thi gian pht phat hoa xung con 10-15 phut, ngi ta thm vao
dung dch pht phat cac cht kh phn cc: mui bisunphit, sunphit hay cac hp
cht hu c: hydroxylamin, nitrobenzen, thioure'.
2.2. Pht phat hoa lanh:
La pht phat hoa nhit thng, khng tn nhit nng, khng cn khng
ch nhit mt cach nghim ngt. Tuy nhin, mang pht phat thu c mong
thng c dung lam nn cho lp sn.
1hanh phn va ch d lam vic:

Dung dch 1:
Majef 35-45g/l
Zn(NO
3
)
2
70-90g/l
NaF 4-6g/l
Thi gian 20-40 phut
Axit chung/Axit t do 10-13
Dung dch 2:
H
3
PO
4
35-45g/l
ZnO 15-17g/l
NaNO
2
4-6g/l
Thi gian 15-20 phut
pH 2-3






PHU LUC

DON VJ & CACH TINH TC D N MON:
Tc n mon c tnh bng mils (1mils 0.001 inch; 1inch 2.54cm)
tc la mc xuyn thung trn mt nm (MPY: penetration per year) co th
tnh theo cng thc sau:

T A D
W
MPY


=
534
(cm/h)
534: hng s
W: khi lng mt i (mg)
D: t khi (g/cm
3
)
A: din tch mu (cm
2
)
T: thi gian (h)

1MPY 0.0254 mm/nm 25.4 m/nm 2.90 nm/h 0.805 pm/s
1m 10
3
mm 10
6
m 10
9
nm 10
12
pm

Bang 8.1. bn n mon
D bn n mon MPY
Khng b n mon <1
c bit 1-5
Tt 5-20
Kha tt 20-50
Kem 50-200
Khng chp nhn c >200













1AI LIU 1HAM KHAO:

1/ W.A. SChultze; Phan Lng Cm. n mon & bao v kim loai. 1985.
2/ Nguyn nh Luyn. n mon va bao v kim loai. NXB Cng nhn ky thut,
1980.
3/ Nguyn nh Ph. n mon va bao v kim loai. NXB T.P. H Ch Minh, 1980.
4/ Nguyn vn Tu. n mon va bao v kim loai. NXB Khoa hoc ky thut, 2001.
5/ H.H. VHLIG. Corrosion and corrosion control. New York, 1971.
6/ L.L. SHREIR. Corrosion I and II. London, 1976.
7/ DENNY A. JONES. Principle and prevention of Corrosion. New York, 1992.
8/ B. COTTIS. Introduction to corrosion. 2002.
9/ M. Pourbaix. Atlas of Electrochemical Equilibria in aqueous Solution. Oxford,
1966.
10/ http://www.cp.umist.ac.uk/CPC/Courses
11/ http://www. umist.ac.uk/corrosion/lecturenotes/Echem





























MUC LUC

CHNG 1: M U
III. Tnh hnh n mon va bao v kim loai cua th gii va Vit Nam.
IV. ai cng n mon
2.3. nh ngha
2.4. Phn loai

CHNG 2: N MON IN HOA
V. Khai nim
5.1. Gii thiu
5.2. Phan ng in hoa
5.3. nh lut Faraday
VI. in th in cc
6.1. Lp in tch kep
6.2. Nguyn nhn xut hin lp in tch kep
6.3. Cac loai in cc so sanh
VII. Phng trnh ng hoc c ban cua qua trnh in cc
7.1. Nng lng hoat hoa t do
7.2. Qua trnh phn cc hoat hoa trang thai cn bng
7.3. Qua trnh phn cc hoat hoa trang thai khng cn bng
VIII. ng hoc cac qua trnh in cc
8.1. Phan ng in cc b khng ch bi giai oan chuyn in tch
8.2. Phan ng in cc b khng ch bi giai oan khuch tan
8.3. S phn cc lin hp

CHNG 3: LY THUYT N MON HN HP

V. C cu n mon in hoa
VI. iu kin nhit ng cua qua trnh n mon
VII. n mon vi s kh phn cc hydro va oxy
7.1. n mon vi s kh phn cc hydro
7.2. n mon vi s kh phn cc oxy
VIII. Ly thuyt in th hn hp


CHNG 4: GIAN IN TH - pH (GIAN POURBAIX)

V. Gii thiu
VI. Gian E-pH cua nc sach 25
o
C
VII. Gian E-pH cua h Fe-H
2
O 25
o
C
VIII. Cng dung cua gian E-pH

CHNG 5: THU NG HOA VA PHNG PHAP BAO V IN HOA

IV. Thu ng hoa kim loai
4.1. Khai nim
4.2. ng hoc cua qua trnh thu ng hoa kim loai
4.3. Bao v ant
V. Bao v in hoa bng cach thay i in th in cc
5.1. Khai nim
5.2. Bao v bng Protector
5.3. Bao v bng dong in ngoai

CHNG 6: NHNG NHN T ANH HNG N TC N MON

III. Nhng nhn t bn trong
1.1. Tnh bn nhit ng cua kim loai
1.2. V tr cua kim loai trong bang h thng tun hoan
IV. Nhng nhn t bn ngoai
2.1. Anh hng cua pH
2.2. Anh hng thanh phn va nng cua dung dch mui
2.3. Anh hng cua nng oxy
5.4. Anh hng cua nhit
5.5. Anh hng cua tc chuyn ng cua dung dch
5.6. Anh hng cua dong in ro
5.7. Anh hng cua cac nhn t khac
VI. Cht lam chm n mon
6.1. Khai nim
6.2. Cht lam chm ant
6.3. Cht lam chm catt
6.4. Cht lam chm hu c
6.5. Cht lam chm bay hi
6.6. Cht lam chm hoa tan trong du m

CHNG 7: LP PHU BAO V

A. Lp phu kim loai
III. C cu
3.1. Lp phu ant
3.2. Lp phu catt
IV. Phng phap phu
4.1. Phng phap in
4.2. Phng phap nhit
B. Lp phu phi kim loai
III. Trang men
3.1. C cu bao v cua lp men
3.2. Nguyn liu san xut men
3.3. Trang men
IV. Sn
4.1. Vai tro cua lp sn
4.2. Yu cu cua mang sn
4.3. Thanh phn cua mang sn
4.4. Qua trnh gia cng mang sn
C. Lp phu cac hp cht yhoa hoc
III. Oxy hoa va nhum mau kim loai
3.1. Oxy hoa kim loai en
3.2. Oxy hoa kim loai mau
IV. Pht phat hoa kim loai
4.1. Pht phat hoa nong
4.2. Pht phat hoa lanh