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GIAO
TRNH
N MON VA BAO V
KIM LOAI
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
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:
1. nh 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 c cu cua qua trnh n mon
- n mon hoa hoc
- n mon in hoa
2.2. Theo iu kin cua qua trnh 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 c trng cua dang n mon (Hnh 1.1)
- n mon u (thep cacbon trong dung dch axit sunphuaric)
- n mon vt, tao thanh nhng vt dai trn b mt (ng thau trong nc
bin)
- n mon di b mt
Hnh 1.1
CHNG 2
N MON IN HOA
I/ Khai nim
1.1. Gii 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+ (l ) + Zn(r ) Cu (r ) + Zn 2+ (l )
Zn ZnSO4
Qua trnh anod
Cu ni
CuSO4 Cu (r)
Qua trnh catod
Zn(r) Zn2+(l)
Cu2+(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
Hnh 2.1.
1.2. Phan ng in 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:
Fe Fe 2+ + 2e
V du:
Hoc
Fe 2+ + 2e Fe
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
Ita
nF
(1)
i: mt dong ( i =
I
).
A
m ia
=
tA nF
(2)
+
+
+
+
+
+
+
+
+
+
+
+
+
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.
G*
G*
Hnh 2.5
vi G = nFE
3.2. Qua trnh phn cc hoat hoa trang thai cn bng:
Nng lng hoat in hoa hoc i vi qua trnh chuyn in tch (k hiu
_____
OX + ne RED
hoc nng lng hoat hoa hoa hoc ( Ga* ) i vi phan ng anod:
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.
Nh vy:
= Ga* nFE
(1)
va
(2)
_____
Kim loai
_____
Ga*
G
*
a
Gc*
_____
*
c
nFE
(1 )nFE
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)
ia = nFf a C RED exp[
______
*
a
G
]
RT
(3)
(ic ) = nFf c C OX
Gc*
exp[
]
RT
(4)
(Ga* nFE )
]
ia = nFf a C RED exp[
RT
(ic ) = nFf c C OX exp{
hay
[Gc* + (1 )nFE ]
}
RT
nFE
RT
(6)
(7)
(1 )nFE
}
RT
Ga*
Gc*
'
'
) va f c = f c exp(
)
Vi f a = f a exp(
RT
RT
(ic ) = nFf c' C OX exp{
(5)
(8)
RED = OX + ne
Nh vy, ta co:
nFf a' C RED exp[
nFE cb
RT
f 'C
nF
exp(
E cb ) = c' OX
RT
f a C RED
(1 )nFE cb
}
RT
f'
C
nF
E cb = ln c' + ln OX
RT
C RED
fa
E cb =
f ' RT C OX
RT
ln c' +
ln
nF
f a nF C RED
(9)
(10)
(11)
(12)
f'
RT C OX
RT
ln c' + ) +
ln
nF C RED
nF
fa
(13)
COX, CRED: nng cht oxy hoa va cht kh tai in cc trang thai cn bng.
iu kin chun: C OX = C RED = 1mol / l
E cb = E 0 (in th in cc chun)
RT C OX
E cb = E 0 +
ln
nF C RED
(14)
gia tr khac, ngha la lam cho E Ecb th luc o mt dong in anod hay catod
se c sinh ra do anh hng cua s di chuyn khoi gia tr Ecb ti nng lng
hoat hoa cua phan ng catod hay anod. Trong trng hp nay ta co:
'
exp[
ia = nFf a' C RED
nFE
RT
'
(ic ) = nFf c' C OX
exp{
(1 )nFE
}
RT
(15)
(16)
'
'
C RED
, C OX
: la nng cht kh va cht oxy hoa tai b mt in cc trang
(ic ) = i0
'
C OX
(1 )nF (E E cb )
exp[
]
C OX
RT
(17)
(18)
Luc nay C RED , C OX : la nng cht kh va cht oxy hoa trong dung dch.
Vi E - Ecb = E - Ecb = th luc nay mt dong in tng itotal in
itotal = ia + ic
cc se la:
Hay
itotal
'
'
C RED
nF C OX
(1 )nF
exp[
]
exp[
]}
= i0 {
C RED
RT
C OX
RT
(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 , CRED, COX, io, .
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 RED
= C RED va C OX
= C OX
Nh vy phng trnh (19) se tr thanh:
itotal = i0 {exp[
nF
RT
] exp[
(1 )nF
]}
RT
(20)
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.)
ia = i0 exp
nF
(21)
RT
ic = i0 exp[
(1 )nF
]
RT
(22)
i=ia + ic > 0
ia
i
ic
i=ia + ic < 0
Hnh 2.7
* Qua th ln (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 nF
log ia = log i0 +
a (>50mV)
(22)
2.303RT
(1 c )nF
log ic = log i0
c (> -50mV)
2.303RT
2.303RT
2.303RT
log i0 +
log ia
Hay: a =
a nF
a nF
2.303RT
2.303RT
c =
log i0
log ic
(1 c )nF
(1 c )nF
(23)
(24)
(25)
(26)
Phng trnh (26) goi la phng trnh Tafel (Hnh 2.8). dc cua ng
thng (log i ) c goi la dc Tafel, c dung xac nh cac thng s ng
hoc cua qua trnh chuyn in tch io, .
Vi ba =
2.303RT
2.303RT
va bc =
a nF
(1 c )nF
ia
io
ic
logi
Hnh 2.8
* Qua th nho, va gia s rng a= c= 0.5
Ta co:
i = i0
nF
RT
Do o, ta co in tr phn cc Rp:
RT
Rp =
nFi0
(27)
(28)
ba bc
2.303(ba + bc ) R p
(29)
Nng
C H0 2
dC
) x =0
dx
C H' 2
khoang cach x
Hnh 2.9.
C : nng ion H trong dung dch
0
H2
act ,c =
i
2.303RT
2.303RT
log i0
log ic = bc log c
(1 c )nF
i0
(1 c )nF
i
2.303RT
log(1 c )
nF
iL
i
i
2.303RT
log(1 c )
= bc log c +
i0
nF
iL
conc =
T ,c
Con i phan ng anod hoa tan kim loai th phn cc nng xem nh
khng ang k (co th bo qua). Do o:
a = ba log
ia
i0
iL
i
nhanh catod
(chuyn in tch khng ch)
nhanh catod
(khuych tan khng ch)
Hnh 2.10.
CHNG 3
LY THUYT N MON HN HP
I/ C cu n mon in hoa:
Kim loai
Vung anod
ne
Cht in li
Men+
Me
K+
Vung catod
ne
D.ne
A-
Hnh 3.1.
Gm 3 qua trnh:
O
Men+.mH2O
1. Qua trnh anod:
ne Me mH
2. Qua trnh chuyn in t tha:
3. Qua trnh catod:
D + ne [D.ne]
2
H cho:
Fe
Fe 2+ + 2e
RT
ln C Fe 2 +
nF
= 0.44 + 0.03 log 10 6 = 0.62V
0
cb
E Fe
= E Fe
+
2+
2+
/ Fe
/ Fe
cb
E Fe
2+
/ Fe
H nhn:
2 H + + 2e
H2
E Hcb+ / H = 0.059 pH
2
cb
H + / H2
= 0.06V
H + .H 2 O + e H + H 2 O
iu kin c ban:
1
H 2 + H 2O
2
3/ Mt phn nguyn t hydro tao thanh hoa tan vao kim loai
4/ Kt hp cac nguyn t hp phu: H hp + H hp = H 2 hay kh hp phu in
hoa:
H hp + H + .H 2 O + e H 2 + H 2 O
5/ Khuych tan cac phn t H2 vao dung dch sau o khuych tan vao
khng kh.
6/ Cac phn t H2 trn b mt catod tp hp lai thanh bot kh va thoat ra
khoi b mt kim loai:
H 2 + H 2 + H 2 + H 2 + H 2 + H 2 + .... = nH 2
Kim loai
Khng kh
5
Dung dch
4
3
2
1
p
Hnh 3.2.
3.1.3. c im cua s kh phn cc 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 vi s kh phn cc oxy:
3.2.1. iu kin nhit ng:
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
O2 + 2 H 2 O + 4e 4OH
oxy:
iu kin c ban:
O2
1
Khng kh
6
Dung dch
2
5
4
p
Hnh 3.3.
IV/ Ly thuyt in th hn hp:
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:
ia,Fe
(1)
Fe
Fe2+ + 2e
ic,Fe
ic,H+
+
H2
(2)
(dd acid)
2H + 2e
ia,H+
ic,H2O
2H2O + 2e
H2 + 2OH-
(2a)
2H2O
(3)
(dd acid)
4OH-
(3a)
ia,H2O
ic,O2
+
O2 + 4H + 4e
ia,O2
ic,O2
O2 + 2H2O + 4e
ia,O2
E(V)
H 2 2 H + + 2e
0.1 -
io , H +
E Hcb+ / H 0.0
2
2 H + + 2e H 2
i0, Fe 2+ / Fe
Fe Fe 2+ + 2e
cb
E Fe
2+
/ Fe
- 0.5 Fe 2+ + 2e Fe
logi
Hnh 3.4.
Hai in th in cc E Hcb
/ H2
cb
va E Fe
2+
/ Fe
E(V)
io , H +
E Hcb+ / H
2 H + + 2e H 2
icorr
E M = E corr
Fe Fe 2+ + 2e
i0, Fe 2+ / Fe
cb
E Fe
2+
/ Fe
logi
Hnh 3.5
.
Vy
Va
Fe nF
cb
( E corr E Fe
)]
RT
(1 H + )nF
exp[
( E corr E Hcb+ )]
RT
Phng trnh ng cong phn cc tng (Hnh 3.5.) cua phan ng n mon:
itotal = ia , Fe + ic , H +
Trong o:
ia , Fe = i0, Fe exp[
Tng t ta co:
Fe nF
cb
( E E corr ) + ( E corr E Fe
)]
RT
nF
nF
cb
ia , Fe = i0, Fe exp[ Fe ( E E corr )] exp[ Fe ( E corr E Fe
)]
RT
RT
nF
ia , Fe = icorr exp[ Fe ( E E corr )]
RT
(1 H + )nF
ic , H + = icorr exp[
( E E corr )]
RT
2.303RT
2.303RT
va c =
a nF
(1 c )nF
nF
RT
RT i
=
nF icorr
i = icorr
hay
di
) =0 =
nFicorr
2 H + + 2e H 2
E corr
Fe Fe 2+ + 2e
cb
E Fe
2+
/ Fe
i
Hnh 3.6.
E(V)
io, H +
E Hcb+ / H
2 H + + 2e H 2
icorr
E corr
Fe Fe 2+ + 2e
i0, Fe 2 + / Fe
cb
E Fe
2+
/ Fe
logi
E(volt)
Hnh 3.7.
H+->H2(M)
H+->H2(N)
-0.1
sum(ic)
-0.2
N->Nn+
M->Mm+
-0.3
sum(ia)
-0.4
-0.5
-0.6
-0.7
-0.8
-0.9
-1
x(i=10E+x)(mA/cm2)
-8
-7
-6
-5
-4
-3
-2
-1
Hnh 3.8.
CHNG 4
GIAN IN TH-pH (POURBAIX)
I/ Gii 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
cb
, E Hcb / H , va E Ocb / H O .
cn bng cua anod va catod ring phn o: E Me
/ Me
+
n+
(1)
(2)
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)2 + 2e
Me + OH 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 E-pH cua nc sach 25oC:
Trong nc sach khi tip xuc vi khng kh, ngoai cac phn t H2O ra con
co mt lng rt nho ion H+ va OH-, cung vi kh hoa tan ma quan trong la la kh
O2 .
H2
* i vi phan ng: 2H+ + 2e
Phan ng trn cung co th vit lai di dang sau (trong mi trng trung tnh hay
kim)
H2
+
2OH2H2O + 2e
( E H0 O / H = 0.83V )
2
/ H2
= 0.059 pH (ng a)
2H2O
Phan ng trn cung co th vit lai di dang sau (trong mi trng trung tnh hay
kim)
4OHO2 + 2H2O + 4e
( EO0 / OH = +0.411V )
2
PO = 1at theo phng trnh NERNST ta co: EOcb = 1.23 0.059 pH (ng b)
2
* i vi phan ng:
H + OH
Vi C H * COH = 14 hay pOH + pH = 14
H2 O
E(V)
2
1.5
O2+4H++4e =2H2O
O2
1
0.5
H+ + OH-=H2O
a
0
-0.5
2H+ + 2e=H2
-1
-1.5
H2
-2
-2
10
12
14
pH
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 E-pH cua h Fe-H2O 25oC:
Ngoai cac cu t k n: H2O, H+, OH-, O2 va H2, con phai k n cac
cu t khac nh: Fe, Fe2+, Fe3+, HFeO2-, 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:
C Fe 2 + (C OH ) = 1.9 10 15 ; C Fe3+ (C OH ) 3 = 7 10 38
2
0
0
E Fe
= 0.44V ; E Fe
= +0.77V
2+
3+
/ Fe
/ Fe 2 +
Bang 4.1.
Phan ng
Phng trnh
E = 0.059 pH
H 2 2 H + 2e
+
2 H 2 O O2 + 4 H + 4e
E = +1.23 0.059 pH
Fe Fe 2+ + 2e
Fe 2+ Fe 3+ + e
Fe 2+ + 2 H 2 O Fe(OH ) 2 + 2 H +
E = +0.77
pH = 6.65 0.5 log( Fe 2+ ) = 9.65
1
pH = +1.613 log( Fe 3+ ) = 3.61
3
E = 0.05 0.059 pH
Fe 3+ + 3H 2 O Fe(OH ) 3 + 3H +
Fe + 2 H 2 O Fe(OH ) 2 + 2 H + + 2e
E = +0.27 0.059 pH
Fe(OH ) 2 + OH Fe(OH ) 3 + e
Fe
2+
+ 3H 2 O Fe(OH ) 3 + 3H + e
E = +1.41 0.177 pH
Fe + 2 H 2 O HFeO + 3H + 3e
E = +0.316 0.0886 pH
Fe(OH ) 2 HFeO2 + H +
HFeO2 Fe(OH ) 3 + 2e
ng 1 c tnh bng:
cb
0
E Fe
= E Fe
+
2+
2+
/ Fe
/ Fe
0.059
log( Fe 2+ ) = 0.44 0.059 3 = 0.62V
2
ng 5 c tnh nh sau:
T phan ng:
Fe Fe 2+ + 2e
0.059
log( Fe 2+ )
2
+ 2 H 2 O Fe(OH ) 2 + 2 H + (2)
Ta co phng trnh:
0
cb
E Fe
= E Fe
+
2+
2+
/ Fe
/ Fe
Vi phan ng:
Fe 2+
Ta co:
TFe ( OH ) 2 = ( Fe 2+ )(OH ) 2
Do o:
Vi:
cb
0
+
E Fe
( OH ) 2 / Fe = E Fe ( OH ) 2 / Fe + 0.059 log( H )
V:
cb
cb
E Fe
( OH ) 2 / Fe = E Fe 2 + / Fe
cb
0
= E Fe
+
E Fe
2+
2+
/ Fe
/ Fe
(1)
TFe ( OH ) 2 / Fe
0.059
log(
)
2
(OH ) 2
ng
a
b
1
2
3
4
5
6
7
8
9
10
cb
0
E Fe
= E Fe
+
2+
2+
/ Fe
/ Fe
0.059
log(TFe (OH ) 2 / Fe ) 0.059 log(OH ) 2
2
0.059
log(TFe ( OH ) 2 / Fe ) + 0.059 14 + 0.059 log( H + )
2
0.059
0
0
E Fe
log(TFe ( OH ) 2 / Fe ) + 0.059 14
Vy:
( OH ) 2 / Fe = E Fe 2 + / Fe +
2
0
Thay s vao ta co: E Fe
( OH ) 2 / Fe == 0.05
cb
0
E Fe
= E Fe
+
2+
2+
/ Fe
/ Fe
hay
E(V)
E = 0.05 0.059 pH
1.5
Fe3+
4
b
Fe(OH)3
0.5
7
Fe2+
a
-0.5
Fe(OH)2
10
9
HFeO2-
5
Fe
-1
-1.5
2
10
12
14
pH
CHNG 5
THU NG HOA VA PHNG PHAP BAO V IN HOA
I/ Thu ng 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 Ao n vai trm Ao va c
hnh thanh do qua trnh oxy hoa.
Fe + 2 H 2 O Fe(OH ) 2 + 2 H + + 2e
V du:
- 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 HNO3.
Tc n mon (g/m2.h)
1000 -
500 -
30 40 50
HNO3(%)
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.
ng hoc cua qua trnh thu ng 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)
xMe + yH 2 O Me x O y + 2 yH + + 2 ye
10
20
a/ Phn cc anod:
V du: Fe b phn cc anod trong dung dch 0.5M H2SO4, bt u phn cc
t in th n mon Ecorr. (Hnh 5.2.)
E(V)
2 H 2 O O2 + 4 H + + 4e
1.25 i pass = 7 10 2 A / m 2
1.00 -
2 Fe + 3H 2 O Fe2 O3 + 6 H + + 6e
+0.5 -
icit = 2 10 3 A / m 2
E Hcb2
0.0 -
2 H + + 2e H 2
FeSO4
-0.25 cb
E Fe
-0.5 -
Fe Fe 2+ + 2e
!
-2
!
0
!
!
2
4
logi
Hnh 5.2.
b/ Nhung kim loai vao cht in li co cht oxy hoa thch hp:
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
cb
dng hn E p . Trong trng hp ta co mt phan ng a in cc vi
bng E redox
in th hn hp ( Ecorr ) c xac nh bng phan ng anod cua kim loai hoc oxyt
kim loai vi phan ng kh cua cht oxy hoa.
Nu tc cua phan ng kh E p ln hn tc phan ng anod ( icrit ) th
kim loai se b thu ng.
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:
cb
cb
> E redox
> Ep
(5a)
1/ E puqtd
2/ ic ,redox
Ep
> icrit
(5b)
vung thu ng
E
cb
redox
E corr
OX RED + ne
EF
Ep
logicrit logic,redox
logipass
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.
Tuy nhin vic bao v anod thng gp mt s kho khn nh 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 in hoa bng cach thay i in th in cc:
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 cc 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 cc 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.
3
2
Gian tip
Trc 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 in ngoai:
Bao v catod bng dong ngoai co th lp t nh sau (Hnh 5.5.)
V
- +
4
Hnh 5.5.
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.
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:
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:
I=
E ccb E acb
R
I phu thuc vao E ccb va E acb , tc phu thuc vao ban cht cua kim loai.
V du: - Trong mi trng trung tnh E Hcb = 0.41V nhng kim loai nao co
2
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.
2.2.
V tr 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/ Nhng nhn t bn ngoai:
2.1.
Anh hng cua pH:
a/Anh hng trc 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 hng 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)
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 Al3+, Zn2+,
Sn2+, Sn4+, ...Trong mi trng kim tao thanh phc cht ZnO22-, AlO2-, ...(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 hng cua thanh phn va nng cua dung dch 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: KClO3, K2CrO4, KNO2, ...Ngc lai nu
mui co tnh oxy hoa la cht kh phn cc th se lam tng tc n mon: S2O82-,...
- Nhng mui co tnh axit hay baz khi tng nng cua no th pH tng
nn co anh hng nh pH: Na2CO3, AlCl3, ...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: MeH2PO4, Me(HPO4)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
t.gian
Hnh 6.2. Tc n mon phu thuc vao
Dang anion co trong dung dch
LiCl
nng
Hnh 6.3. Tc n mon phu thuc
vao dang cation va nng cua mui
2.3.
Anh hng cua nng 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
12
18
24
cm3/l
Hnh 6.4.
2.4.
Anh hng cua nhit :
Nhit anh hng ln n tc n mon. Trong dung dch in li tc
n mon tng khi tng nhit .
6
Hnh 6.5.
T
2.5.
Anh hng cua tc chuyn ng dung dch:
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 hng cua dong in 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
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):
Z=
K 0 K1
(%)
K0
Ko: Tc n mon kim loai trong dung dch cha co CLC (g/m2.h).
K1: Tc n mon kim loai trong dung dch khi co CLC (g/m2.h).
+ Hiu qua bao v ():
=
K0
(%)
K0
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: Na2CrO4, NaNO2, hn hp cua (NaNO2 + NaCO3), ...
V du: Cromat hoa b mt st, thep:
O
O
Cr
Cr
O
Fe
O
Cr
O
Fe
O
Cr
O
Cr
O
Cr
O
Cr
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: Na2SO3, Ca(HCO3)2, NH2NH2, ZnSO4, ... Ngoai ra, cung co mt s ion kim loai nh As3+, Bi3+ 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 hu c:
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.
3.5.
Cht lam chm bay hi:
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.
Nhng c trng quan trong cua CLC bay hi la:
+ Phbh = 10-210-4 mmHg 2025oC.
+ Co tac dung bao v kim loai lam vic trong khng gian kn.
Tac dung cua CLC bay hi:
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.
Phng phap s dung CLC bay hi:
+ Cho CLC bay hi trong khng gian kn: phong, hom kn.
+ Quet CLC bay hi trn giy bao goi.
Mt s CLC bay hi thng c s dung:
+ CLC phtphat, loai nay thng c dung bao v thep, gang, crom,
niken, thic. Phi liu nh sau:
77% NaNO2 + 5.5% (NH4)2HPO4 + 1% Na2CO3 (trong lng)
Hn hp nay dang bt, cho vao bao b va c 1m3 khng gian cn 1.5kg
bt.
+ CLC bay hi trn c s natrinitrit va benzoat.
32.5% Benzoat + 16.5% NaNO2 + 1% (NH4)2CO3 (trong lng)
3.6. Cht lam chm hoa tan trong du m:
CHNG 7
LP 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. Lp phu kim loai:
I. C cu:
1.1.
Lp 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.
Lp 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. Phng phap phu:
2.1. Phng phap in: s dung ngun in mt chiu
Ban cht cua phng phap nay la kt tua in hoa t cac kim loai khac.
R
+ -
Zn
Fe
Hnh 7.1.
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:
2
3
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. Lp 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.
C cu bao v cua lp 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:
* u im:
- 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.
* Nhc im:
- 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.
NaOH
NaNO3
Ch oxy hoa
138-140oC
(khi nhung) 20-120 phut
142-146oC
(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 H3PO4 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.
4-10
70-100
1.0-2.0
-
4-10
70-100
1.0-2.0
8-10
-
Nhit
2-10
70-100
1.0-2.0
30-40
100oC
Thi gian
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 ng:
Oxy hoa ng chng n mon, trang tr trong cng nghip va thit b quang hoc.
a. Oxy hoa theo phng 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
15 g/l
K2S2O8
Nhit
60-65oC
Thi gian
5 phut
b. Oxy hoa theo phng phap in 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
80-90oC (Cu)
60-70 oC (ng thau)
0.5 A/dm2
ia
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:
CuSO4
50 g/l
NaOH
35 g/l
30 g/l
C2H2O4
pH
9.2-9.6
Nhit
20-32oC
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 phng 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:
50 g/l
Na2CO3
NaOH
2-2.5 g/l
15 g/l
Na2CrO4
Nhit
80-100oC
Thi gian
5-30 phut
b. Oxy hoa theo phng phap in hoa:
- C cu tao mang oxyt:
+ Qua trnh anod:
(1)
Al Al3+ + 3e
(2)
OH- O2 + H2O + 4e
Qua trnh nay co th chia lam nhiu giai oan:
2OH- O2- + H2O
O2- O- + e
O- O + e
2O O2
2Al3+ + 3O2- Al2O3
(3)
(4)
2Al + 3O
Al2O3
+ Qua trnh catt:
H+ + 2e H2
(5)
Nhm khi mi cho vao dung dch in li co th xay ra phan ng sau:
(6)
2Al + 3H2SO4 Al2(SO4)3 + 3H2
Dong mt chiu
180-200
15-23
1.5-2
0.8-1.2
12-13
13-28
40-50
Chu y: mun co mang oxyt day, chu mai mon phai oxy hoa trong dung dch lanh
13oC, ia =22.3 A/dm2, thi gian = 34 h.
1.2.3. Nhum mau nhm va hp 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 K2Cr2O4 thi gian khoang 30 phut, ra
sach, sau o em nhung vao trong dung dch 50100g/l AgNO3 cung trong thi
gian 30 phut. Mau cua mang oxyt se xut hin do phan ng sau
K2Cr2O4 + AgNO3 = Ag2Cr2O4 + 2KNO3
vang da cam
Bang 7.4. Thanh phn dung dch khi nhum mau cac hp cht v c.
Mau
nhum
Dung dch 1
Nng
Mui
(g/l)
Xanh
FeCl2
10-100
Da lng CuSO4
10-100
Vang
Pb(CH3COO)2 100-200
Trng
Pb(CH3COO)2 10-50
Vang anh Na2SO3
10-50
en
Co(CH3COO)2 10-100
Dung dch 2
Mui
Nng
(g/l)
K4Fe(CN)6
10-50
K4Fe(CN)6
10-50
K2Cr2O7
50-100
Na2SO4
10-50
KMnO4
10-50
KMnO4
15-25
Hp cht
mau
Xanh da tri
CuFe(CN)6
PbCr2O7
PbSO4
MnO
CoO
Bang 7.5. Thanh phn dung dch khi nhum mau cac hp cht hu c.
Tn cht mau
Alizarin vang
Vang da cam cho nhm
Mau tm cho nhm
Vang 53 cho nhm
Xanh cho nhm
Alizarin o
Nng (g/l)
5
1-3
1
1
1
2
Nhit (oC)
50
20-25
50-60
50-60
50-60
50-60
pH
4-5
4-7
6-7
3-4
1.2.4. S mach:
A
+ -
Al
Pb
Pb
H2SO4
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 (400-500oC) mang pht phat cung khng chu c lu.
2.1.
Pht phat hoa nong:
2.1.1. Pht phat hoa thng:
Nhung mu thep vao dung dch mui pht phat dang hoa tan, thng s
dung la mui Majef: Mn(H2PO4)2.H2O, Mn(HPO4), Fe(H2PO4)2 hay monophotphat
Zn. Co dang tng quat nh sau: Me(H2PO4)2
Mui nay nhit thng b phn huy nhng khng ang k:
Me( H 2 PO4 ) 2 Me( HPO4 ) + H 3 PO4
(1)
un nong se phn huy trit hn:
(2)
Khi nhung thep vao dung dch pht phat se xay ra hai qua trnh sau:
Fe Fe 2+
* Qua trnh ant:
* Qua trnh catt: 2 H + + 2e H 2
Ion H+ do s phn li cua H3PO4 t do hay do cac phan ng sau:
Me( H 2 PO4 ) 2 Me 2+ + 2 H 2 PO4
(3)
H 2 PO4 H + + HPO42
HPO
2
4
H + PO
3
4
(4)
(5)
(7)
Zn 2+ + HPO42 = ZnHPO4
(8)
(9)
(10)
(11)
Thi gian pht phat hoa khoang 35-50 phut, nhit dung dch duy tr
khoang 96-98oC. Nhit cao, mui se b phn huy theo phan ng (1) va (2). Do
o, MeHPO4 va Me3(PO4)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 (SO42-, Cl-)
- T s axit chung va axit t do.
axit t do c xac nh bng phep chun vi metyldacam. C
10ml dung dch th mt 3-4ml NaOH 0.1N
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.
Thanh phn va ch lam vic:
Majef
32g/l
Nhit
98-100oC
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.
Thanh phn va ch lam vic:
Dung dch 1:
Majef
Zn(NO3)2
NaF
Thi gian
Axit chung/Axit t do
Dung dch 2:
H3PO4
ZnO
NaNO2
Thi gian
pH
35-45g/l
70-90g/l
4-6g/l
20-40 phut
10-13
35-45g/l
15-17g/l
4-6g/l
15-20 phut
2-3
PHU LUC
N V & CACH TNH TC 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:
MPY =
534 W
D AT
(cm/h)
534: hng s
W: khi lng mt i (mg)
D: t khi (g/cm3)
A: din tch mu (cm2)
T: thi gian (h)
1MPY = 0.0254 mm/nm = 25.4 m/nm = 2.90 nm/h = 0.805 pm/s
1m = 103 mm = 106 m = 109 nm = 1012 pm
Bang 8.1. bn n mon
bn n mon
Khng b n mon
c bit
Tt
Kha tt
Kem
Khng chp nhn c
MPY
<1
1-5
5-20
20-50
50-200
>200
MUC LUC
CHNG 1: M U
I.
II.
Tnh hnh n mon va bao v kim loai cua th gii va Vit Nam.
ai cng n mon
2.1. nh ngha
2.2. Phn loai
IV.
IV.
C cu n mon in hoa
iu kin nhit ng cua qua trnh n mon
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
Ly thuyt in th hn hp
Gii thiu
Gian E-pH cua nc sach 25oC
Gian E-pH cua h Fe-H2O 25oC
Cng dung cua gian E-pH
II.
II.
III.
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
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:
3. nh 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 c cu cua qua trnh n mon
- n mon hoa hoc
- n mon in hoa
2.4. Theo iu kin cua qua trnh 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 c trng cua dang n mon (Hnh 1.1)
- n mon u (thep cacbon trong dung dch axit sunphuaric)
- n mon vt, tao thanh nhng vt dai trn b mt (ng thau trong nc
bin)
- n mon di b mt
Hnh 1.1
CHNG 2
N MON IN HOA
I/ Khai nim
1.1. Gii 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+ (l ) + Zn(r ) Cu (r ) + Zn 2+ (l )
Zn ZnSO4
Qua trnh anod
Cu ni
CuSO4 Cu (r)
Qua trnh catod
Zn(r) Zn2+(l)
Cu2+(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
Hnh 2.1.
1.2. Phan ng in 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:
Fe Fe 2+ + 2e
V du:
Hoc
Fe 2+ + 2e Fe
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
Ita
nF
(1)
i: mt dong ( i =
I
).
A
m ia
=
tA nF
(2)
+
+
+
+
+
+
+
+
+
+
+
+
+
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.
G*
G*
Hnh 2.5
vi G = nFE
3.2. Qua trnh phn cc hoat hoa trang thai cn bng:
Nng lng hoat in hoa hoc i vi qua trnh chuyn in tch (k hiu
_____
OX + ne RED
hoc nng lng hoat hoa hoa hoc ( Ga* ) i vi phan ng anod:
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.
Nh vy:
= Ga* nFE
(1)
va
(2)
_____
Kim loai
_____
G a*
G
*
a
Gc*
_____
*
c
nFE
(1 )nFE
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)
ia = nFf a C RED exp[
______
*
a
G
]
RT
(3)
(ic ) = nFf c C OX
Gc*
exp[
]
RT
(4)
(G a* nFE )
ia = nFf a C RED exp[
]
RT
(ic ) = nFf c C OX exp{
hay
[Gc* + (1 )nFE ]
}
RT
nFE
RT
(6)
(7)
(1 )nFE
}
RT
Ga*
Gc*
'
'
) va f c = f c exp(
)
Vi f a = f a exp(
RT
RT
(ic ) = nFf c' C OX exp{
(5)
(8)
RED = OX + ne
Nh vy, ta co:
nFf a' C RED exp[
nFE cb
RT
f 'C
nF
exp(
E cb ) = c' OX
RT
f a C RED
(1 )nFE cb
}
RT
f'
C
nF
E cb = ln c' + ln OX
C RED
RT
fa
E cb =
f ' RT C OX
RT
ln c' +
ln
nF
f a nF C RED
(9)
(10)
(11)
(12)
f'
RT
RT C OX
ln c' + ) +
ln
nF
nF C RED
fa
(13)
COX, CRED: nng cht oxy hoa va cht kh tai in cc trang thai cn bng.
iu kin chun: COX = C RED = 1mol / l
E cb = E 0 (in th in cc chun)
RT C OX
ln
E cb = E 0 +
nF C RED
(14)
gia tr khac, ngha la lam cho E Ecb th luc o mt dong in anod hay catod
se c sinh ra do anh hng cua s di chuyn khoi gia tr Ecb ti nng lng
hoat hoa cua phan ng catod hay anod. Trong trng hp nay ta co:
'
ia = nFf a' C RED
exp[
nFE
RT
'
(ic ) = nFf c' C OX
exp{
(1 )nFE
}
RT
(15)
(16)
'
'
C RED
, C OX
: la nng cht kh va cht oxy hoa tai b mt in cc trang
(ic ) = i0
'
C OX
(1 )nF (E E cb )
exp[
]
C OX
RT
(17)
(18)
Luc nay C RED , COX : la nng cht kh va cht oxy hoa trong dung dch.
Vi E - Ecb = E - Ecb = th luc nay mt dong in tng itotal in
itotal = ia + ic
cc se la:
Hay
itotal
'
'
C RED
(1 )nF
nF C OX
= i0 {
exp[
]
exp[
]}
C RED
RT
C OX
RT
(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 , CRED, COX, io, .
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 RED
= C RED va C OX
= C OX
Nh vy phng trnh (19) se tr thanh:
itotal = i0 {exp[
nF
RT
] exp[
(1 )nF
]}
RT
(20)
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.)
ia = i0 exp
nF
(21)
RT
ic = i0 exp[
(1 )nF
]
RT
(22)
i=ia + ic > 0
ia
i
ic
i=ia + ic < 0
Hnh 2.7
* Qua th ln (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 nF
a (>50mV)
(22)
log ia = log i0 +
2.303RT
(1 c )nF
c (> -50mV)
log ic = log i0
2.303RT
2.303RT
2.303RT
log i0 +
log ia
Hay: a =
a nF
a nF
2.303RT
2.303RT
log i0
log ic
c =
(1 c )nF
(1 c )nF
(23)
(24)
(25)
(26)
Phng trnh (26) goi la phng trnh Tafel (Hnh 2.8). dc cua ng
thng (log i ) c goi la dc Tafel, c dung xac nh cac thng s ng
hoc cua qua trnh chuyn in tch io, .
Vi ba =
2.303RT
2.303RT
va bc =
a nF
(1 c )nF
ia
io
ic
logi
Hnh 2.8
* Qua th nho, va gia s rng a= c= 0.5
Ta co:
i = i0
nF
RT
Do o, ta co in tr phn cc Rp:
RT
Rp =
nFi0
(27)
(28)
ba bc
2.303(ba + bc ) R p
(29)
Nng
C H0 2
dC
) x =0
dx
C H' 2
khoang cach x
Hnh 2.9.
C : nng ion H trong dung dch
0
H2
iL
act ,c =
i
2.303RT
2.303RT
log i0
log ic = bc log c
i0
(1 c )nF
(1 c )nF
i
2.303RT
log(1 c )
nF
iL
i
i
2.303RT
= bc log c +
log(1 c )
i0
nF
iL
conc =
T ,c
Con i phan ng anod hoa tan kim loai th phn cc nng xem nh
khng ang k (co th bo qua). Do o:
a = ba log
ia
i0
iL
i
nhanh catod
(chuyn in tch khng ch)
nhanh catod
(khuych tan khng ch)
Hnh 2.10.
CHNG 3
LY THUYT N MON HN HP
I/ C cu n mon in hoa:
Kim loai
Vung anod
ne
Cht in li
Men+
Me
K+
Vung catod
ne
D.ne
A-
Hnh 3.1.
Gm 3 qua trnh:
O
Men+.mH2O
1. Qua trnh anod:
ne Me mH
2. Qua trnh chuyn in t tha:
3. Qua trnh catod:
D + ne [D.ne]
2
H cho:
Fe
Fe 2+ + 2e
RT
ln C Fe 2 +
nF
= 0.44 + 0.03 log 10 6 = 0.62V
cb
0
E Fe
= E Fe
+
2+
2+
/ Fe
/ Fe
cb
E Fe
2+
/ Fe
H nhn:
2 H + + 2e
H2
E Hcb+ / H = 0.059 pH
2
cb
H + / H2
= 0.06V
H + .H 2 O + e H + H 2 O
iu kin c ban:
1
H 2 + H 2O
2
3/ Mt phn nguyn t hydro tao thanh hoa tan vao kim loai
4/ Kt hp cac nguyn t hp phu: H hp + H hp = H 2 hay kh hp phu in
hoa:
H hp + H + .H 2 O + e H 2 + H 2 O
5/ Khuych tan cac phn t H2 vao dung dch sau o khuych tan vao
khng kh.
6/ Cac phn t H2 trn b mt catod tp hp lai thanh bot kh va thoat ra
khoi b mt kim loai:
H 2 + H 2 + H 2 + H 2 + H 2 + H 2 + .... = nH 2
Kim loai
Khng kh
5
Dung dch
4
3
2
1
p
Hnh 3.2.
3.1.3. c im cua s kh phn cc 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 vi s kh phn cc oxy:
3.2.1. iu kin nhit ng:
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
O2 + 2 H 2 O + 4e 4OH
oxy:
iu kin c ban:
O2
1
Khng kh
6
Dung dch
2
5
4
p
Hnh 3.3.
IV/ Ly thuyt in th hn hp:
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:
ia,Fe
(1)
Fe
Fe2+ + 2e
ic,Fe
ic,H+
+
H2
(2)
(dd acid)
2H + 2e
ia,H+
ic,H2O
2H2O + 2e
H2 + 2OH-
(2a)
2H2O
(3)
(dd acid)
4OH-
(3a)
ia,H2O
ic,O2
+
O2 + 4H + 4e
ia,O2
ic,O2
O2 + 2H2O + 4e
ia,O2
E(V)
H 2 2 H + + 2e
0.1 -
io , H +
E Hcb+ / H 0.0
2
2 H + + 2e H 2
i0, Fe 2+ / Fe
Fe Fe 2+ + 2e
cb
E Fe
2+
/ Fe
- 0.5 Fe 2+ + 2e Fe
logi
Hnh 3.4.
Hai in th in cc E Hcb
/ H2
cb
va E Fe
2+
/ Fe
E(V)
io , H +
E Hcb+ / H
2 H + + 2e H 2
icorr
E M = E corr
Fe Fe 2+ + 2e
i0, Fe 2+ / Fe
cb
E Fe
2+
/ Fe
logi
Hnh 3.5
.
Vy
Va
Fe nF
cb
( E corr E Fe
)]
RT
(1 H + )nF
exp[
( E corr E Hcb+ )]
RT
Phng trnh ng cong phn cc tng (Hnh 3.5.) cua phan ng n mon:
itotal = ia , Fe + ic , H +
Trong o:
ia , Fe = i0, Fe exp[
Tng t ta co:
Fe nF
cb
( E E corr ) + ( E corr E Fe
)]
RT
nF
nF
cb
)]
ia , Fe = i0, Fe exp[ Fe ( E E corr )] exp[ Fe ( E corr E Fe
RT
RT
nF
ia , Fe = icorr exp[ Fe ( E E corr )]
RT
(1 H + )nF
ic , H + = icorr exp[
( E E corr )]
RT
2.303RT
2.303RT
va c =
a nF
(1 c )nF
nF
RT
RT i
=
nF icorr
i = icorr
hay
di
) =0 =
nFicorr
2 H + + 2e H 2
E corr
Fe Fe 2+ + 2e
cb
E Fe
2+
/ Fe
i
Hnh 3.6.
E(V)
io , H +
E Hcb+ / H
2 H + + 2e H 2
icorr
E corr
Fe Fe 2+ + 2e
i0, Fe 2+ / Fe
cb
E Fe
2+
/ Fe
logi
E(volt)
Hnh 3.7.
H+->H2(M)
H+->H2(N)
-0.1
sum(ic)
-0.2
N->Nn+
M->Mm+
-0.3
sum(ia)
-0.4
-0.5
-0.6
-0.7
-0.8
-0.9
-1
x(i=10E+x)(mA/cm2)
-8
-7
-6
-5
-4
-3
-2
-1
Hnh 3.8.
CHNG 4
GIAN IN TH-pH (POURBAIX)
I/ Gii 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
cb
, E Hcb / H , va E Ocb / H O .
cn bng cua anod va catod ring phn o: E Me
/ Me
+
n+
(1)
(2)
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)2 + 2e
Me + OH 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 E-pH cua nc sach 25oC:
Trong nc sach khi tip xuc vi khng kh, ngoai cac phn t H2O ra con
co mt lng rt nho ion H+ va OH-, cung vi kh hoa tan ma quan trong la la kh
O2 .
H2
* i vi phan ng: 2H+ + 2e
Phan ng trn cung co th vit lai di dang sau (trong mi trng trung tnh hay
kim)
H2
+
2OH2H2O + 2e
( E H0 O / H = 0.83V )
2
/ H2
= 0.059 pH (ng a)
2H2O
Phan ng trn cung co th vit lai di dang sau (trong mi trng trung tnh hay
kim)
4OHO2 + 2H2O + 4e
( EO0 / OH = +0.411V )
2
PO = 1at theo phng trnh NERNST ta co: EOcb = 1.23 0.059 pH (ng b)
2
* i vi phan ng:
H + OH
Vi C H * COH = 14 hay pOH + pH = 14
H2 O
E(V)
2
1.5
O2+4H++4e =2H2O
O2
1
0.5
H+ + OH-=H2O
a
0
-0.5
2H+ + 2e=H2
-1
-1.5
H2
-2
-2
10
12
14
pH
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 E-pH cua h Fe-H2O 25oC:
Ngoai cac cu t k n: H2O, H+, OH-, O2 va H2, con phai k n cac
cu t khac nh: Fe, Fe2+, Fe3+, HFeO2-, 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:
C Fe 2 + (C OH ) = 1.9 10 15 ; C Fe3+ (C OH ) 3 = 7 10 38
2
0
0
E Fe
= 0.44V ; E Fe
= +0.77V
2+
3+
/ Fe
/ Fe 2 +
Bang 4.1.
Phan ng
Phng trnh
E = 0.059 pH
H 2 2 H + 2e
+
2 H 2 O O2 + 4 H + 4e
E = +1.23 0.059 pH
Fe Fe 2+ + 2e
Fe 2+ Fe 3+ + e
Fe 2+ + 2 H 2 O Fe(OH ) 2 + 2 H +
E = +0.77
pH = 6.65 0.5 log( Fe 2+ ) = 9.65
1
pH = +1.613 log( Fe 3+ ) = 3.61
3
E = 0.05 0.059 pH
Fe 3+ + 3H 2 O Fe(OH ) 3 + 3H +
Fe + 2 H 2 O Fe(OH ) 2 + 2 H + + 2e
E = +0.27 0.059 pH
Fe(OH ) 2 + OH Fe(OH ) 3 + e
Fe
2+
+ 3H 2 O Fe(OH ) 3 + 3H + e
E = +1.41 0.177 pH
Fe + 2 H 2 O HFeO + 3H + 3e
E = +0.316 0.0886 pH
Fe(OH ) 2 HFeO2 + H +
HFeO2 Fe(OH ) 3 + 2e
ng 1 c tnh bng:
0
cb
E Fe
= E Fe
+
2+
2+
/ Fe
/ Fe
0.059
log( Fe 2+ ) = 0.44 0.059 3 = 0.62V
2
ng 5 c tnh nh sau:
T phan ng:
Fe Fe 2+ + 2e
0.059
log( Fe 2+ )
2
+ 2 H 2 O Fe(OH ) 2 + 2 H + (2)
Ta co phng trnh:
0
cb
E Fe
= E Fe
+
2+
2+
/ Fe
/ Fe
Vi phan ng:
Fe 2+
Ta co:
TFe ( OH ) 2 = ( Fe 2+ )(OH ) 2
Do o:
Vi:
cb
0
+
E Fe
( OH ) 2 / Fe = E Fe ( OH ) 2 / Fe + 0.059 log( H )
V:
cb
cb
E Fe
( OH ) 2 / Fe = E Fe 2 + / Fe
0
cb
E Fe
= E Fe
+
2+
2+
/ Fe
/ Fe
(1)
TFe ( OH ) 2 / Fe
0.059
log(
)
2
(OH ) 2
ng
a
b
1
2
3
4
5
6
7
8
9
10
cb
0
E Fe
= E Fe
+
2+
2+
/ Fe
/ Fe
0.059
log(TFe (OH ) 2 / Fe ) 0.059 log(OH ) 2
2
0.059
log(TFe ( OH ) 2 / Fe ) + 0.059 14 + 0.059 log( H + )
2
0.059
0
0
E Fe
log(TFe ( OH ) 2 / Fe ) + 0.059 14
Vy:
( OH ) 2 / Fe = E Fe 2 + / Fe +
2
0
Thay s vao ta co: E Fe
( OH ) 2 / Fe == 0.05
cb
0
E Fe
= E Fe
+
2+
2+
/ Fe
/ Fe
hay
E(V)
E = 0.05 0.059 pH
1.5
Fe3+
4
b
Fe(OH)3
0.5
7
Fe2+
a
-0.5
Fe(OH)2
10
9
HFeO2-
5
Fe
-1
-1.5
2
10
12
14
pH
CHNG 5
THU NG HOA VA PHNG PHAP BAO V IN HOA
I/ Thu ng 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 Ao n vai trm Ao va c
hnh thanh do qua trnh oxy hoa.
Fe + 2 H 2 O Fe(OH ) 2 + 2 H + + 2e
V du:
- 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 HNO3.
Tc n mon (g/m2.h)
1000 -
500 -
30 40 50
HNO3(%)
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.
ng hoc cua qua trnh thu ng 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)
xMe + yH 2 O Me x O y + 2 yH + + 2 ye
10
20
a/ Phn cc anod:
V du: Fe b phn cc anod trong dung dch 0.5M H2SO4, bt u phn cc
t in th n mon Ecorr. (Hnh 5.2.)
E(V)
2 H 2 O O2 + 4 H + + 4e
1.25 i pass = 7 10 2 A / m 2
1.00 -
2 Fe + 3H 2 O Fe2 O3 + 6 H + + 6e
+0.5 -
icit = 2 10 3 A / m 2
E Hcb2
0.0 -
2 H + + 2e H 2
FeSO4
-0.25 cb
E Fe
-0.5 -
Fe Fe 2+ + 2e
!
-2
!
0
!
!
2
4
logi
Hnh 5.2.
b/ Nhung kim loai vao cht in li co cht oxy hoa thch hp:
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
cb
dng hn E p . Trong trng hp ta co mt phan ng a in cc vi
bng E redox
in th hn hp ( E corr ) c xac nh bng phan ng anod cua kim loai hoc oxyt
kim loai vi phan ng kh cua cht oxy hoa.
Nu tc cua phan ng kh E p ln hn tc phan ng anod ( icrit ) th
kim loai se b thu ng.
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:
cb
cb
> E redox
> Ep
(5a)
1/ E puqtd
2/ ic ,redox
Ep
> icrit
(5b)
vung thu ng
E
cb
redox
E corr
OX RED + ne
EF
Ep
logicrit logic,redox
logipass
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.
Tuy nhin vic bao v anod thng gp mt s kho khn nh 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 in hoa bng cach thay i in th in cc:
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 cc 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 cc 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.
3
2
Gian tip
Trc 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 in ngoai:
Bao v catod bng dong ngoai co th lp t nh sau (Hnh 5.5.)
V
- +
4
Hnh 5.5.
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.
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:
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:
I=
E ccb E acb
R
I phu thuc vao E ccb va E acb , tc phu thuc vao ban cht cua kim loai.
V du: - Trong mi trng trung tnh E Hcb = 0.41V nhng kim loai nao co
2
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.
2.2.
V tr 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/ Nhng nhn t bn ngoai:
2.1.
Anh hng cua pH:
a/Anh hng trc 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 hng 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)
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 Al3+, Zn2+,
Sn2+, Sn4+, ...Trong mi trng kim tao thanh phc cht ZnO22-, AlO2-, ...(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 hng cua thanh phn va nng cua dung dch 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: KClO3, K2CrO4, KNO2, ...Ngc lai nu
mui co tnh oxy hoa la cht kh phn cc th se lam tng tc n mon: S2O82-,...
- Nhng mui co tnh axit hay baz khi tng nng cua no th pH tng
nn co anh hng nh pH: Na2CO3, AlCl3, ...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: MeH2PO4, Me(HPO4)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
t.gian
Hnh 6.2. Tc n mon phu thuc vao
Dang anion co trong dung dch
LiCl
nng
Hnh 6.3. Tc n mon phu thuc
vao dang cation va nng cua mui
2.3.
Anh hng cua nng 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
12
18
24
cm3/l
Hnh 6.4.
2.4.
Anh hng cua nhit :
Nhit anh hng ln n tc n mon. Trong dung dch in li tc
n mon tng khi tng nhit .
6
Hnh 6.5.
T
2.5.
Anh hng cua tc chuyn ng dung dch:
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 hng cua dong in 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
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):
Z=
K 0 K1
(%)
K0
Ko: Tc n mon kim loai trong dung dch cha co CLC (g/m2.h).
K1: Tc n mon kim loai trong dung dch khi co CLC (g/m2.h).
+ Hiu qua bao v ():
=
K0
(%)
K0
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: Na2CrO4, NaNO2, hn hp cua (NaNO2 + NaCO3), ...
V du: Cromat hoa b mt st, thep:
O
O
Cr
Cr
O
Fe
O
Cr
O
Fe
O
Cr
O
Cr
O
Cr
O
Cr
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: Na2SO3, Ca(HCO3)2, NH2NH2, ZnSO4, ... Ngoai ra, cung co mt s ion kim loai nh As3+, Bi3+ 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 hu c:
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.
3.5.
Cht lam chm bay hi:
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.
Nhng c trng quan trong cua CLC bay hi la:
+ Phbh = 10-210-4 mmHg 2025oC.
+ Co tac dung bao v kim loai lam vic trong khng gian kn.
Tac dung cua CLC bay hi:
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.
Phng phap s dung CLC bay hi:
+ Cho CLC bay hi trong khng gian kn: phong, hom kn.
+ Quet CLC bay hi trn giy bao goi.
Mt s CLC bay hi thng c s dung:
+ CLC phtphat, loai nay thng c dung bao v thep, gang, crom,
niken, thic. Phi liu nh sau:
77% NaNO2 + 5.5% (NH4)2HPO4 + 1% Na2CO3 (trong lng)
Hn hp nay dang bt, cho vao bao b va c 1m3 khng gian cn 1.5kg
bt.
+ CLC bay hi trn c s natrinitrit va benzoat.
32.5% Benzoat + 16.5% NaNO2 + 1% (NH4)2CO3 (trong lng)
3.6. Cht lam chm hoa tan trong du m:
CHNG 7
LP 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. Lp phu kim loai:
I. C cu:
1.1.
Lp 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.
Lp 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. Phng phap phu:
2.1. Phng phap in: s dung ngun in mt chiu
Ban cht cua phng phap nay la kt tua in hoa t cac kim loai khac.
R
+ -
Zn
Fe
Hnh 7.1.
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:
2
3
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. Lp 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.
C cu bao v cua lp 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:
* u im:
- 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.
* Nhc im:
- 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.
NaOH
NaNO3
Ch oxy hoa
138-140oC
(khi nhung) 20-120 phut
142-146oC
(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 H3PO4 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.
4-10
70-100
1.0-2.0
-
4-10
70-100
1.0-2.0
8-10
-
Nhit
2-10
70-100
1.0-2.0
30-40
100oC
Thi gian
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 ng:
Oxy hoa ng chng n mon, trang tr trong cng nghip va thit b quang hoc.
a. Oxy hoa theo phng 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
15 g/l
K2S2O8
Nhit
60-65oC
Thi gian
5 phut
b. Oxy hoa theo phng phap in 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
80-90oC (Cu)
60-70 oC (ng thau)
0.5 A/dm2
ia
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:
CuSO4
50 g/l
NaOH
35 g/l
30 g/l
C2H2O4
pH
9.2-9.6
Nhit
20-32oC
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 phng 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:
50 g/l
Na2CO3
NaOH
2-2.5 g/l
15 g/l
Na2CrO4
Nhit
80-100oC
Thi gian
5-30 phut
b. Oxy hoa theo phng phap in hoa:
- C cu tao mang oxyt:
+ Qua trnh anod:
(1)
Al Al3+ + 3e
(2)
OH- O2 + H2O + 4e
Qua trnh nay co th chia lam nhiu giai oan:
2OH- O2- + H2O
O2- O- + e
O- O + e
2O O2
2Al3+ + 3O2- Al2O3
(3)
(4)
2Al + 3O
Al2O3
+ Qua trnh catt:
H+ + 2e H2
(5)
Nhm khi mi cho vao dung dch in li co th xay ra phan ng sau:
(6)
2Al + 3H2SO4 Al2(SO4)3 + 3H2
Dong mt chiu
180-200
15-23
1.5-2
0.8-1.2
12-13
13-28
40-50
Chu y: mun co mang oxyt day, chu mai mon phai oxy hoa trong dung dch lanh
13oC, ia =22.3 A/dm2, thi gian = 34 h.
1.2.3. Nhum mau nhm va hp 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 K2Cr2O4 thi gian khoang 30 phut, ra
sach, sau o em nhung vao trong dung dch 50100g/l AgNO3 cung trong thi
gian 30 phut. Mau cua mang oxyt se xut hin do phan ng sau
K2Cr2O4 + AgNO3 = Ag2Cr2O4 + 2KNO3
vang da cam
Bang 7.4. Thanh phn dung dch khi nhum mau cac hp cht v c.
Mau
nhum
Dung dch 1
Nng
Mui
(g/l)
Xanh
FeCl2
10-100
Da lng CuSO4
10-100
Vang
Pb(CH3COO)2 100-200
Trng
Pb(CH3COO)2 10-50
Vang anh Na2SO3
10-50
en
Co(CH3COO)2 10-100
Dung dch 2
Mui
Nng
(g/l)
K4Fe(CN)6
10-50
K4Fe(CN)6
10-50
K2Cr2O7
50-100
Na2SO4
10-50
KMnO4
10-50
KMnO4
15-25
Hp cht
mau
Xanh da tri
CuFe(CN)6
PbCr2O7
PbSO4
MnO
CoO
Bang 7.5. Thanh phn dung dch khi nhum mau cac hp cht hu c.
Tn cht mau
Alizarin vang
Vang da cam cho nhm
Mau tm cho nhm
Vang 53 cho nhm
Xanh cho nhm
Alizarin o
Nng (g/l)
5
1-3
1
1
1
2
Nhit (oC)
50
20-25
50-60
50-60
50-60
50-60
pH
4-5
4-7
6-7
3-4
1.2.4. S mach:
A
+ -
Al
Pb
Pb
H2SO4
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 (400-500oC) mang pht phat cung khng chu c lu.
2.1.
Pht phat hoa nong:
2.1.1. Pht phat hoa thng:
Nhung mu thep vao dung dch mui pht phat dang hoa tan, thng s
dung la mui Majef: Mn(H2PO4)2.H2O, Mn(HPO4), Fe(H2PO4)2 hay monophotphat
Zn. Co dang tng quat nh sau: Me(H2PO4)2
Mui nay nhit thng b phn huy nhng khng ang k:
Me( H 2 PO4 ) 2 Me( HPO4 ) + H 3 PO4
(1)
un nong se phn huy trit hn:
(2)
Khi nhung thep vao dung dch pht phat se xay ra hai qua trnh sau:
Fe Fe 2+
* Qua trnh ant:
* Qua trnh catt: 2 H + + 2e H 2
Ion H+ do s phn li cua H3PO4 t do hay do cac phan ng sau:
Me( H 2 PO4 ) 2 Me 2+ + 2 H 2 PO4
(3)
H 2 PO4 H + + HPO42
HPO
2
4
H + PO
3
4
(4)
(5)
(7)
Zn 2+ + HPO42 = ZnHPO4
(8)
(9)
(10)
(11)
Thi gian pht phat hoa khoang 35-50 phut, nhit dung dch duy tr
khoang 96-98oC. Nhit cao, mui se b phn huy theo phan ng (1) va (2). Do
o, MeHPO4 va Me3(PO4)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 (SO42-, Cl-)
- T s axit chung va axit t do.
axit t do c xac nh bng phep chun vi metyldacam. C
10ml dung dch th mt 3-4ml NaOH 0.1N
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.
Thanh phn va ch lam vic:
Majef
32g/l
Nhit
98-100oC
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.
Thanh phn va ch lam vic:
Dung dch 1:
Majef
Zn(NO3)2
NaF
Thi gian
Axit chung/Axit t do
Dung dch 2:
H3PO4
ZnO
NaNO2
Thi gian
pH
35-45g/l
70-90g/l
4-6g/l
20-40 phut
10-13
35-45g/l
15-17g/l
4-6g/l
15-20 phut
2-3
PHU LUC
N V & CACH TNH TC 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:
MPY =
534 W
D AT
(cm/h)
534: hng s
W: khi lng mt i (mg)
D: t khi (g/cm3)
A: din tch mu (cm2)
T: thi gian (h)
1MPY = 0.0254 mm/nm = 25.4 m/nm = 2.90 nm/h = 0.805 pm/s
1m = 103 mm = 106 m = 109 nm = 1012 pm
Bang 8.1. bn n mon
bn n mon
Khng b n mon
c bit
Tt
Kha tt
Kem
Khng chp nhn c
MPY
<1
1-5
5-20
20-50
50-200
>200
MUC LUC
CHNG 1: M U
III.
IV.
Tnh hnh n mon va bao v kim loai cua th gii va Vit Nam.
ai cng n mon
2.3. nh ngha
2.4. Phn loai
C cu n mon in hoa
iu kin nhit ng cua qua trnh n mon
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
Gii thiu
Gian E-pH cua nc sach 25oC
Gian E-pH cua h Fe-H2O 25oC
Cng dung cua gian E-pH
V.
IV.
VI.
6.5.
6.6.