Amkl - Chuong 3 - Anmondienhoa 1

I HC QUC GIA TP.
HCM
TRNG I HC BCH KHOA
Bi ging
N MN V BO V VT LIU
(CORROSION AND MATERIALS PROTECTION)
CHNG 3.
N MN IN HA HC (I)
CHNG 3. N MN IN HA HC
Trng i hc Bch Khoa i hc Quc gia TP. HCM
3.1. Khi nim

n mn in ha hc: s ph hy kim loi bi cc
phn ng in ha xy ra trong mi trng dn
in
L dng n mn nguy him v ph bin trong sn

xut v i sng;
Xy ra trong mi trng t nhin: nc, khng
kh, t.
CHNG
N MN
IN
1.1.3.Khi
nim
vHA
n HC
mn
kim loi
3.1. Khi nim

in cc n
H in ho gm cht dn in loi 1 tip xc vi
cht dn in loi 2, trn mt gii hn pha ch xy ra
mt phn ng in ha.
V d: Kim loi Cu nhng trong dung dch cha h oxy
ho kh cha Cu2+. Phn ng in cc l:
Cu2+ + 2e- Cu
Th cn bng Ecb cn c gi l th thun nghch
hoc l th dng.
4
CHNG
N MN
IN
1.1.3.Khi
nim
vHA
n HC
mn
kim loi
3.1. Khi nim

V d: Nhng thanh Cu vo dung dich
CuSO4. Phn ng in cc l:
Cu2+ + 2e- Cu
in cc n
CHNG
N MN
IN
1.1.3.Khi
nim
vHA
n HC
mn
kim loi
3.1. Khi nim

Khi c s phn cc in cc bng dng ngoi hoc
bng khp kn mch in, th in cc Ei b dch ra khi
th cn bng Ecb, lch ny c gi l phn cc
in cc v thng c k hiu l E hoc (qu th)
E = = Ei Ecb
Nu > 0 phn cc anod
< 0 - s phn cc catod
Phn ng n mn in ha hc kim loi xy ra khi
G = -nFEpin < 0
trong : n: s in t trao i
F : hng s Faraday (F=96.500 C = 96.500 A.s)
Epin: in th ca pin n mn(V)
Epin= Ecatod Eanod > 0, do : Ecatod > Eanod
6
CHNG
N MN
IN
1.1.3.Khi
nim
vHA
n HC
mn
kim loi
3.1. Khi nim

in cc hn hp
H in ho gm cht dn in loi 1 tip xc vi

cht dn in loi 2, song trn b mt gii hn pha
thng xy ra nhiu phn ng in cc v t nht c
hai h oxy ho kh xy ra v mt hnh thc.

V d: Kim loi ng nhng vo dung dch CuSO4 c
mt H+ v oxy.
CHNG
N MN
IN
1.1.3.Khi
nim
vHA
n HC
mn
kim loi
3.1. Khi nim
V d: Kim loi ng nhng

vo dung dch CuSO4 c
mt H+ v oxy.
in cc hn hp
8
CHNG
N MN
IN
1.1.3.Khi
nim
vHA
n HC
mn
kim loi
3.1. Khi nim
Phn ng anod:
Cu Cu2+ + 2ePhn ng catod:
O2 + 2H+ + 2e- H2O
Phn ng tng:
Cu +()O2 + 2H+ Cu2+ + H2O
Gi tr in th o c khi phn ng tng t n trng
thi cn bng c gi l in th n mn ca in cc Cu
(Ecorr).
CHNG
N MN
IN
1.1.3.Khi
nim
vHA
n HC
mn
kim loi
3.2. Nhit ng hc qu trnh n mn in ha hc

Cch tip cn qu trnh n mn in ha hc:
Nhit ng hc: xc nh kh nng phn ng n
mn xy ra
Ha l: xc nh c ch ca phn ng n mn
ng hc: xc nh tc ca phn ng n mn
Qu trnh luyn kim nh hng n bn n mn
10

n mn in ha xy ra khi kim loi tip xc vi
dung dch cht in ly l s ph hy kim loi xy

ra trn mt gii hn 2 pha kim loi v dung dch
cht in ly:
Kim loi b ha tan trn vng anod v km theo
phn ng gii phng hydro hoc tiu th oxy xy
ra trn vng catod, sinh ra dng in

Do c s xut hin v hot ng ca pin n mn
11
Ni cch khc, n mn in ha l qu trnh in

cc trng thi khng cn bng
H n mn nh mt nguyn t Galvanic
B mt kim loi phi c dung dch in ly vn

chuyn ion trn b mt dung dch
12
CHNG
3. Nnim
MNv
IN
1.1. Khi
n HA
mnHC
kim loi

Chuyn sang h in ha:
Trong mt phn ng ha hc, cn xem xt n th in
ha
Thut ng ha th th hin mc nng lng in tng
tc vi mi trng
= +
Vi
n s e- trao i
F hng s Faraday
th Galvanic
13
CHNG
3. Nnim
MNv
IN
1.1. Khi
n HA
mnHC
kim loi

Xt hai kim loi tip xc nhau ( v ):
c mt e- cn bng gia hai kim loi
14
CHNG
3. Nnim
MNv
IN
1.1. Khi
n HA
mnHC
kim loi

Do e- v tr cn bng
=
V
= c gi l bc nhy th
15
CHNG
3. Nnim
MNv
IN
1.1. Khi
n HA
mnHC
kim loi

Trong mt qu trnh in ha, cn c s tip xc
ca mt kim loi v mt dung dch, electron cn t
c trng thi cn bng gia kim loi (M) v dung
dch (dd)
Odd + eM Rdd
16
CHNG
3. Nnim
MNv
IN
1.1. Khi
n HA
mnHC
kim loi

O + e, = R
O + nO Fdd + e, F = R + nR Fdd
Lu : M l do s electron trao i l -1
Hay O + e, R = nR nO F + F
M nO nR = 1
Nn M,dd = dd =
O +e, R
F
= o + RTln(a)
o
Suy ra M, = M,
+
RT
a
ln o
nF
aR
17
CHNG
3. Nnim
MNv
IN
1.1. Khi
n HA
mnHC
kim loi
Trong thc t, dung dch thng c nng ph

hp c th s dng nng thay cho hot .
Khi :
Suy ra
o
M, = M,
+
RT
O
ln
nF
R
18
CHNG
3. Nnim
MNv
IN
1.1. Khi
n HA
mnHC
kim loi
Bc nhy th l gi tr KHNG O C
Tuy nhin, c th s dng mt in cc th
hai t vo trong dung dch xc nh sc
in ng E (s khc bit ca hai th

Galvanic)
19
CHNG
3. Nnim
MNv
IN
1.1. Khi
n HA
mnHC
kim loi

=
Hay = +
Phn ng tng cng:
O2 + R1 R2 + O1
in cc 1: O1 + e- R1
in cc 2: O2 + e- R2
20
CHNG
3. Nnim
MNv
IN
1.1. Khi
n HA
mnHC
kim loi

Ti cn bng E = 0 th
0=
1/K
=
=
Nh vy =
21
CHNG
N MN
IN
1.1.3.Khi
nim
vHA
n HC
mn
kim loi
3.3. Phng trnh Nersnt

Phng trnh Nersnt vit cho trng hp phn ng:
aA + bB + ne- cC + dD
in th cn bng:

= +

.
a hot ca ion
Eo Th in cc tiu chun, V
R Hng s kh (R = 8,31J.mol-1.K-1)
T Nhit tuyt i, K
F Hng s Faraday (F= 96.500 A.s)
Chuyn sang logarit, phng trnh Nersnt thnh:

,
= +

22
CHNG
N MN
IN
1.1.3.Khi
nim
vHA
n HC
mn
kim loi

Phng trnh Nersnt i vi kim loi
Mn+ + ne- M
=
+ /
+
+ = + / +
+
+ - hot ion kim loi trong dung dch
+ / - th in cc tiu chun ca kim loi ng vi hot
dung dch bng 1 hoc p sut kh bng 1 atm

23
CHNG
N MN
IN
1.1.3.Khi
nim
vHA
n HC
mn
kim loi

Lu :
+ Cht rn, cht lng c hot bng 1
+ Cht kh c hot bng p sut ring phn ca n
+ Khng th xc nh c gi tr tuyt i ca bt k
th in cc no m phi o th in cc so vi th
ca mt in cc so snh.
+ Cc in cc so snh: in cc hydro chun SHE,
in cc calomel bo ha SCE,
+ Theo quy c, Eo H+/H = 0 V

24
CHNG
N MN
IN
1.1.3.Khi
nim
vHA
n HC
mn
kim loi
3.4. Gin Pourbaix

Do Marcel Pourbaix lp, cn gi l gin E pH
Biu din s ph thuc ca gi tr th in cc vi gi tr pH
mi trng phn ng
Cho thy nhit ng hc ca cc pha khc nhau di cc
iu kin khc nhau
Cc ng bin trn gin phn chia cc khu vc bn ca
cc pha s c tnh theo phng trnh Nernst.
Cho bit cc phn ng v cc sn phm phn ng s hin
din khi phn ng t n cn bng, c bit l cc iu
kin m phn ng n mn khng th xy ra v mt nhit
ng.
25
CHNG
N MN
IN
1.1.3.Khi
nim
vHA
n HC
mn
kim loi
3.4. Gin Pourbaix

c im:
Ch kho st nc, oxy v oxyde (ang pht trin cc

gin cho lu hunh)
Ch p dng vi kim loi, khng s dng cho hp kim
Khng cho bit ng hc ca qu trnh (tc phn

ng)
C th da vo gin iu chnh th hay pH, hn
ch phn ng n mn theo nhit ng trong mt s

trng hp
26
CHNG
N MN
IN
1.1.3.Khi
nim
vHA
n HC
mn
kim loi
3.4. Gin Pourbaix

Tnh ton:
Gin ca nc tinh khit 25oC
Nc l cht in ly rt yu:
2H2O H3O+ + OHNng H+ v OH- rt nh
2H+ + 2e H2
2H2O + 2e H2 + 2OHp dng phng trnh Nernst:
25oC: + / =
(1)
(2)
(3)
+ /
Nu PH2 = 1 atm
(4)
+ / = ,
Phng trnh (4) c th hin trn on thng OA
27
CHNG
N MN
IN
1.1.3.Khi
nim
vHA
n HC
mn
kim loi
3.4. Gin Pourbaix

PH2 > 1 atm on thng OA
dch chuyn v pha m ng
vi O1A1 v s kh ion H+
chim u th, phn ng
dch chuyn v pha phi.
Ngc li, khi PH2 < 1 th
on OA dch chuyn v
pha dng ng vi on
thng O2A2
Gin E - pH i vi h
H2O, H+, OH, O2 25oC vi
PH2 = 1 atm, PO2 = 1atm
28
CHNG
N MN
IN
1.1.3.Khi
nim
vHA
n HC
mn
kim loi
3.4. Gin Pourbaix

Hoc
25oC:
O2 + 4e + 4H+ 2H2O
O2 + 4e + 2H2O 4OH-
/ = / +
(5)
(6)
,
+ .
(7)
Khi PO2 = 1 atm, s ph thuc E pH theo phng trnh (2), ng

vi on BC
Nu PO2 > 1 atm, on BC dch chuyn v pha dng, ng vi
B2C2, (6) dch chuyn v bn tri, nc d b phn hy thnh oxy
Nu PO2 <1 atm, on BC dch chuyn v pha m, ng vi B1C1,
phn hy nc thnh oxy kh khn

Vng BCAO, nc trng thi bn vng
29
CHNG
N MN
IN
1.1.3.Khi
nim
vHA
n HC
mn
kim loi
3.4. Gin Pourbaix

Gin E pH ca kim loi tip xc vi nc
V d:
Fe H2O
Cu t lin quan: H2O, H+, OH, O2 v H2, Fe, Fe2+, Fe3+,
HFeO2 , Fe(OH)3, Fe(OH)2
Al H2O
Cu t lin quan: H2O, H+, OH, O2 v H2, Al, Al3+,
Al(OH)3, Al(OH)4-
30
CHNG
N MN
IN
1.1.3.Khi
nim
vHA
n HC
mn
kim loi
3.4. Gin Pourbaix

Gin Pourbaix ca Fe H2O
Ti nhit 25oC, P = 1 atm
31
CHNG
N MN
IN
1.1.3.Khi
nim
vHA
n HC
mn
kim loi
3.4. Gin Pourbaix

T gin E pH ca Fe H2O:
D on kh nng b n mn v khng b n mn ca st
trong mi trng nc (khng th hin tc n mn)
Nguyn tc ca phng php in ho bo v chng n
mn st trong mi trng nc:
+ Dch chuyn th in cc Fe trong mi trng
nc v pha m hn so vi th n mn ca Fe Fe
vng an ton khng b n mn - nguyn tc bo v catod
+ Dch chuyn th in cc ca Fe trong mi trng
trng nc v pha dng so vi th n mn lm cho kim
loi b th ng - gi l bo v anod
+ iu chnh tng pH ca mi trng n mn a kim
loi vo vng th ng lm gim tc n mn kim loi 32
CHNG
N MN
IN
1.1.3.Khi
nim
vHA
n HC
mn
kim loi
Gin Pourbaix ca Al
3.4. Gin Pourbaix
33
CHNG
N MN
IN
1.1.3.Khi
nim
vHA
n HC
mn
kim loi
Gin Pourbaix ca Zn
3.4. Gin Pourbaix
34
CHNG
N MN
IN
1.1.3.Khi
nim
vHA
n HC
mn
kim loi
Gin Pourbaix ca Pt
3.4. Gin Pourbaix
35
CHNG
N MN
IN
1.1.3.Khi
nim
vHA
n HC
mn
kim loi
3.4. Gin Pourbaix
Ha th = G
Ha th ph thuc vo cu trc pha rn/cht ha tan
36
3.5. C ch n mn in ha hc kim loi

Trn b mt kim loi tn ti vng anod v catod l
so s chnh lch th trn b mt gii hn pha
S chnh lch ny c th do s tn ti ca ph
gia hp kim, do s lch mng tinh th kim loi

Vng anod: kim loi b ha tan, xy ra qu trnh oxy
ha:
M Mn+ + neIon kim loi trn b mt in cc chuyn vo dung
dch
37

Cc electron d vng anod c dch chuyn
n vng catod trn b mt kim loi:
- Mi trng c ion H+
nH+ + ne- (n/2)H2

n mn kim loi km theo gii phng hydro
- Mi trng c ion H+ v oxy:
(n/4)O2 + ne- + nH+ (n/2)H2O

n mn km theo s tiu th oxy c mt trong dung
dch
38

a. Vng anod:
- Ha tan kim loi, li electron trn in cc

- Chuyn ion t b mt kim loi vo th tch dung dch
b. Vng catod:
- Chuyn cc phn t tch in t dung dch n lp dd st
b mt nh khuch tn do chnh lch nng , in di,
- Kh lp v solvat ha ca phn t tch in

- Ion H+ phng in: 2H+ + 2e H2
- Hp ph sn phm trn b mt in cc
- Chuyn sn phm vo dung dch
39

Amkl - Chuong 3 - Anmondienhoa 1

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I HC QUC GIA TP.

3.1. Khi nim

L dng n mn nguy him v ph bin trong sn

Trng i hc Bch Khoa i hc Quc gia TP. HCM

3.1. Khi nim

Trng i hc Bch Khoa i hc Quc gia TP. HCM

3.1. Khi nim

Trng i hc Bch Khoa i hc Quc gia TP. HCM

3.1. Khi nim

Trng i hc Bch Khoa i hc Quc gia TP. HCM

3.1. Khi nim

H in ho gm cht dn in loi 1 tip xc vi

hai h oxy ho kh xy ra v mt hnh thc.

Trng i hc Bch Khoa i hc Quc gia TP. HCM

3.1. Khi nim

V d: Kim loi ng nhng

Trng i hc Bch Khoa i hc Quc gia TP. HCM

3.1. Khi nim

Trng i hc Bch Khoa i hc Quc gia TP. HCM

3.2. Nhit ng hc qu trnh n mn in ha hc

Qu trnh luyn kim nh hng n bn n mn

3.2. Nhit ng hc qu trnh n mn in ha hc

dung dch cht in ly l s ph hy kim loi xy

ra trn vng catod, sinh ra dng in

3.2. Nhit ng hc qu trnh n mn in ha hc

Ni cch khc, n mn in ha l qu trnh in

B mt kim loi phi c dung dch in ly vn

3.2. Nhit ng hc qu trnh n mn in ha hc

3.2. Nhit ng hc qu trnh n mn in ha hc

3.2. Nhit ng hc qu trnh n mn in ha hc

3.2. Nhit ng hc qu trnh n mn in ha hc

3.2. Nhit ng hc qu trnh n mn in ha hc

3.2. Nhit ng hc qu trnh n mn in ha hc

Trong thc t, dung dch thng c nng ph

3.2. Nhit ng hc qu trnh n mn in ha hc

in ng E (s khc bit ca hai th

3.2. Nhit ng hc qu trnh n mn in ha hc

Phn ng tng cng:

3.2. Nhit ng hc qu trnh n mn in ha hc

Trng i hc Bch Khoa i hc Quc gia TP. HCM

3.3. Phng trnh Nersnt

Trng i hc Bch Khoa i hc Quc gia TP. HCM

3.3. Phng trnh Nersnt

+ - hot ion kim loi trong dung dch

+ / - th in cc tiu chun ca kim loi ng vi hot

dung dch bng 1 hoc p sut kh bng 1 atm

Trng i hc Bch Khoa i hc Quc gia TP. HCM

3.3. Phng trnh Nersnt

+ Theo quy c, Eo H+/H = 0 V

Trng i hc Bch Khoa i hc Quc gia TP. HCM

3.4. Gin Pourbaix

Trng i hc Bch Khoa i hc Quc gia TP. HCM

3.4. Gin Pourbaix

Ch kho st nc, oxy v oxyde (ang pht trin cc

Khng cho bit ng hc ca qu trnh (tc phn

ch phn ng n mn theo nhit ng trong mt s

Trng i hc Bch Khoa i hc Quc gia TP. HCM

3.4. Gin Pourbaix

Trng i hc Bch Khoa i hc Quc gia TP. HCM

3.4. Gin Pourbaix

Trng i hc Bch Khoa i hc Quc gia TP. HCM

3.4. Gin Pourbaix

Khi PO2 = 1 atm, s ph thuc E pH theo phng trnh (2), ng