BM CNHH i hc Nng Lm HCM

Gio trnh n mn & Bo v kim loi

Chng III: N MN IN HA
I. MT S KHI NIM
1. n mn in ha
Khi nghin cu mt pin Cu Zn trong dung dch in ly ngi ta nhn thy km b n
mn do din tng anod ha tan : Zn 2e = Zn2+. Cc phn ng in cc xy ra nh sau:

Trong thc t qu trnh n mn xy ra trn cng mt kim loi, ngha l ng thi c c

qu trnh anod v catod, a n s ph hy kim loi:

Nh vy, trn b mt kim loi c rt nhiu catod v anod gn nhau to thnh h thng vi
pin nhiu cc, ta gi l n mn in ha.
n mn in ha l qu trnh n mn m trong pht sinh ra dng in. V vy, n mn
in ha ch xy ra khi kim loi tip xc vi mi trng in ly.
2. Phn ng in ha
a. Cc qu trnh in cc
Anod: qu trnh oxi ha cht kh (kim loi M) thnh dng oxi ha (cation Mn+).
M = Mn+ + ne
Catod: qu trnh kh cht oxi ha (O2 hoc H+,) thnh cht kh.
Ox + ne = Kh
Nu cht oxi ha l H+ th qu trnh xy ra ti catod s l: H+ + e = Hhp
Hhp + Hhp = H2
Nu cht oxi ha l O2 th:
Vi mi trng acid:
O2 + 4H+ + 4e = 2H2O
Vi mi trng trung tnh hoc baz: O2 + 2H2O + 4e = 4OH-.
Th in cc theo phng trnh Nernst:

RT
lg a Ox
(III.1)
nF
a Kh
Trong : R: hng s kh l tng, R = 8,314 J/mol.K
T: nhit tuyt i (K)
F: hng s Faraday, F = 96500 C/mol.
aox, akh: hot ca dng oxi ha v dng kh trng thi cn bng.
E E

BM CNHH i hc Nng Lm HCM

Gio trnh n mn & Bo v kim loi

Bng III.1: Th in cc chun 25oC ca mt s phn ng in cc

b. Phn ng in ha
K thut in ha c s dng rng ri trong k thut v i sng. Tuy nhin, trong n
mn v trong ngnh m in vn cn quan tm l c tnh ca b mt phn chia pha
gia kim loi dung dch, v d: tc phn ng ti b mt, tnh cht ca lp mng trn b
mt hoc hnh dng ca b mt. Cng c kho st v nghin cu cc tnh cht trn l th
v dng. T hai thng s ny chng ta c th suy lun mi th xy ra trn b mt phn chia
pha. Khi chng ta nhng mt thanh kim loi vo dung dch in ly th kim loi c khuynh
hng phn ng vi dung dch in ly : kim loi c th ha tan to thnh cation hoc
cc cation trong dung dch c th kt ta thnh kim loi:
V d:
Fe = Fe2+ + 2e
Hoc
Fe2+ + 2e = Fe
Kt qu ca nhng phn ng ny l kim loi c khuynh hng tch t in tch m hoc
dng. S tch t nhng in tch ny s lm thay i in th ca kim loi v ti gi tr in
th m tc ca hai phn ng t cn bng c gi l in th cn bng.
Mt iu quan trng, khi cho mt mnh kim loi vo dung dch in ly in th cn
bng ca n, iu ny khng c ngha l tc ha tan kim loi v phn ng kt ta kim loi
l bng khng. Phn ng in ha lun lun l mt qu trnh chuyn in tch, ngha l hai
qu trnh kh v oxi ha xy ra ng thi vi tc bng nhau.
c. nh lut Faraday
10

BM CNHH i hc Nng Lm HCM

Gio trnh n mn & Bo v kim loi

Cc phn ng in ha hoc sn xut ra electron hoc tiu th electron. Dng electron

c o bng cng dng in I (A). Theo nh lut Faraday, t l gia khi lng cht
phn ng m vi dng I c xc nh nh sau:

MIt
nF

(III.2)

Trong : F: hng s Faraday, F = 96500 C/mol.

n: s electron trao i.
M: khi lng nguyn t
t: thi gian (s)
Chia phng trnh (III.2) cho thi gian t v din tch b mt in cc A, ta xc nh c
tc n mn r:

m
iM

St
nF

(III.3)

Trong mt dng i = I/S.

Phng trnh (III.3) ch ra t l gia khi lng kim loi mt i trn mt n v din tch
trong mt n v thi gian (v d mg/dm2/ngy) v mt dng i (v d: mA/cm2).
3. Phng trnh ng hc in ha trn in cc n
Trong trng hp tng qut, trn b mt gii hn pha ca in cc xy ra phn ng in
ha.
Ox + ne

vc
Red

va

(III.5)
trng thi cn bng th tc phn ng thun vc bng tc phan ng nghch va. Trong
in ha s dng khi nim dng in hoc mt dng thay cho tc phn ng
I

dq
nFv
dt

(III.6)

Trong : I: cng dng in i qua bnh in phn (qua in cc).

dq: bin thin ca in lng
dt: bin thin ca thi gian (pht, gi)
v: tc phn ng ha hc (mol.m-2.s-1)
n: s electron trao i trong phn ng in ha
F: s Faraday (F = 96493 C)
Tc phn ng thun ca phn ng (III.5) gi l phn ng catod v Ic = nFvc
(III.7a)
Tc phn ng nghch ca phn ng (5) gi l phn ng anod v Ia = nFva (III.7b)
Trong in ha thng dng i lng mt dng in i (A/cm2) thay cho cng
dng in I (A) v bng: i = I/S (A.cm-2, A.m-2), trong S l in tch in cc (cm2, m2).
Vy tc phn ng catod v anod c biu din qua mt dng tng ng l ic v ia.
Tc phn ng in ha (5) c biu din nh sau:
Gc*

ic nFk c C ox exp
RT
Ga*

ia nFk a C red exp

RT
11

(III.8a)
(III.8b)

BM CNHH i hc Nng Lm HCM

Gio trnh n mn & Bo v kim loi

Hnh III.1: Gin quan h G* v th in cc E trn mt gii hn pha ca in cc kim

loi dung dch in li
Trong Gc* v Ga* gi l nng lng hot ng ha in ha i vi phn ng catod
v anod, n quan h cht ch vi s tn ti ca lp in kp trn mt gii hn pha ca in
cc, ngha l vi th in cc.
Trn Hnh III.1 trnh by mi quan h gia Gc* v Ga* v th in cc. Go l nng
lng hot ng ha ng vi trng thi cn bng ca phn ng (III.5).
Khi c s phn cc dng vi th in cc E th cng tch in A bng:
A = nFE
Khi qu trnh anod xy ra phn ng red ox + ne. V d kim loi chuyn thnh ion
kim loi i vo dung dch s d dng hn vi nng lng hot ng ha Ga* v bng:
Ga* = Go - nFE
(III.9)
i vi qu trnh catod, s chuyn ha cc phn t oxi ha (ox) thnh dng kh (red) t
dung dch n in cc s kh khn hn (v d chuyn ion kim loi thnh kim loi Mn+ + ne
M).
Vi nng lng hot ng ha bng Gc*:
Gc* = Go (1- )nFE = Go - nFE
(III.10)
Cc h s v gi l h s chuyn in tch v + = 1. Kt hp cc phng trnh
(8a), (8b), (9), (10) ta c:
G o nFE

ia nFk a C red exp

(III.11)
RT

G
nFE
exp
ia nFk a C red exp

RT
RT
nFE
ia nFK a C red exp

RT

Hoc

Trong :

G o
K a k a exp
RT

Mt cch tng t:

(III.12)

nFE
ic nFK c C ox exp

RT

12

(III.13)

BM CNHH i hc Nng Lm HCM

Gio trnh n mn & Bo v kim loi

G o
K c k c exp
RT

Trong :

T cc phng trnh (III.12), (III.13) cho thy tc phn ng in ha ngoi s ph

thuc vo nng cht phn ng cn ph thuc vo th in cc.
Nu phn ng (III.5) xy ra iu kin cn bng, ng vi th in cc l Ecb th phng
trnh ng hc ca phn ng anod v catod c th hin nh sau:
nFE cb
o
ia nFK a C red
exp
(III.14)

RT
nFE cb
ic nFK c C oxo exp

RT

(III.15)

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

nFE cb
nFE cb
o
io = nFK a C red
exp
= nFK c C oxo exp
(III.16)

o
ox
o
red

RT K c RT C
ln

ln
nF K a nF C

Suy ra:

E cb

Vy:

E cb E cbo

Khi

RT

RT

(III.17)

RT C oxo
ln o
nF C red

(III.18)

C oxo
o
1 th Ecb = E cb gi l th in cc tiu chun.
o
C red

Kt hp cc phng trnh (16) v (18) rt ra:

o1
o1
io nFK a1 .K c .C red
.C oxo nFK so .C oxo .C red
(III.19)
o
1

Trong K S K a .K c , khi cn bng Kc = Ka, mt khc gi tr KSo khng ph thuc vo

th in cc.
Vy dng trao i io khng hon ton l c trng duy nht cho ng hc ca phn ng
in ha m cn ph thuc vo nng cht phn ng.
t ioo l mt dng trao i tiu chun: ioo = nFKSo
(III.20)

o
io ioo .C oxo .C red
Vy
(III.21)
Trong ng hc in ha trao i electron th i lng dng io l mt thng s rt quan
trng v n c quan h cht ch vi tc phn ng oxi ha kh no xy ra trn b mt
kim loi nht nh.
i vi mt h oxi ha kh nht nh, khi xy ra trn cc b mt kim loi khc nhau s
ng vi cc gi tr dng trao i io khc nhau i vi h oxi ha kh nghin cu, ngha l
dng trao i io ca mt h oxi ha kh ph thuc vo bn cht kim loi. V vy, c th dng
gi tr io l thc o kh nng xc tc ca vt liu c dng lm in cc.
4. Gin th in cc pH
Gin th in cc pH trnh by s ph thuc ca gi tr th in cc vo gi tr pH
ca mi trng phn ng. Gin ny c xy dng trn c s cc s liu nhit ng hc
v cho php gii thch trng thi tn ti, tnh cht ca n cht v hp cht cng nh kh
nng chuyn ha gia cc cht c trong h kho st.
S n mn kim loi theo c ch in ha xy ra trong mi trng nc lun gn lin vi
hai qu trnh: s oxi ha kim loi ti anod chuyn kim loi thnh ion kim loi v lun gn

13

BM CNHH i hc Nng Lm HCM

Gio trnh n mn & Bo v kim loi

lin vi phn ng kh xy ra trn catod (s kh ion H3O+ c trong dung dch, kh oxi ha
tan trong dung dch, hoc kh nc).
Mt khc, s n mn kim loi theo c ch in ha ph thuc vo gi tr th in cc ca
anod v catod. Trong mi trng nc cc gi tr th in cc ph thuc ch yu vo pH. V
vy, vic xy dng gin th in cc cn bng pH l cn thit v gi tt l gin th
in cc pH ( E pH ). M. Pourbaix l ngi u tin a ra gin ny (1945) nn gin
E pH cn c gi l gin M. Pourbaix.
a. Gin ca nc tinh khit 25oC
Vic nghin cu gin E pH ca nc rt c ngha i vi s n mn kim loi theo
c ch in ha.
Nc l mt cht in ly rt yu: 2H2O H3O+ + OH- (III.22)
V vy nng H+ v OH- rt nh, trong nc c mt lng kh O2 ha tan ( n gin
ta thay H3O+ bng H+).
Cc phng trnh oxi ha kh c lin quan n H+, OH- v H2O:
2H+ + 2e H2
(23)
2H2O + 2e H2 + 2OH(III.24)
Phn ng (III.23) v (III.24) l cc phn ng in ha dng hn hp.
Phng trnh Nernst p dng cho phn ng (III.23) c dng:
2

25oC:

E 2 H / H E 2oH / H
2

a
0,059
log H
2
PH 2

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

(III.25)
E 2 H / H 0,059 pH

Phng trnh ny cng ng cho phn ng (III.24).

S c mt ca oxi ng vai tr rt quan trng trong n mn kim loi mi trng trung
tnh. Trong trng hp ny, s ha tan ca kim loi thp xy ra trn anod lun gn lin vi
phn ng catiod s tiu th oxi theo phn ng:
O2 + 4e + 4H+ 2H2O (III.26)
Hoc
O2 + 4e + 2H2O 4OH- (III.27)
Phn ng (26) xy ra trn in cc oxi, th in cc c tnh theo phng trnh Nernst
v c gi tr sau:
0,059
log a H4 .PO2 (III.28)
4
0,059
EO2 / H 2O 1,228 0,059 pH
log PO2 (III.29)
4
E O2 / H 2O 1,228 0,059 pH (III.30)
Nu PO2 = 1 atm th
E O2 / H 2O E Oo 2 / H 2O

14

BM CNHH i hc Nng Lm HCM

Gio trnh n mn & Bo v kim loi

Hnh III.2: Gin E pH i vi h H2O, H+, OH- 25oC vi PH2 = 1 atm, PO2 = 1 atm.
Nu mt h c th cn bng m hn th cn bng ca h hydro ( vng A ) th khi tip
xc vi nc dng kh ca h s y H2 ra khi nc.
Nu mt h c th cn bng dng hn th cn bng ca h oxy ( vng C ) th khi tip
xc vi nc dng oxy ha ca h s y O 2 ra khi nc.
Vng A v C v vy l vng khng bn v phng din nhit ng ca nc.
Nu h c th cn bng nm trong vng B th n khng th kh H+ thnh hydro, v
cng khng th oxy ha O2- thnh oxy. H s khng tc dng vi nc. V vy,
vng B l vng bn v mt nhit ng ca nc. T gin E-pH ca H2O ta thy
cc ng EANOD f(pH) , ECATOD f(pH) u chuyn dch tuyn tnh nhau, lun cch
nhau mt on khng i.
Ti mt pH nht nh E = const = (1.22 0.189) = 1.031V. Cng t gin E-pH
ca H2O, khong E = 1.031V cng chnh l khong th m nc khng b phn hy.
b. Gin Fe H2O
St l thnh phn chnh ca cc hp kim thp c s dng rt rng ri trong cc ngnh
cng nghip ch to my cng nh trong cng nghip xy dng. Vic nghin cu nhng vn
lin quan n st, thp c ngha nht nh i vi thc t.
thit lp gin th E pH ca h Fe H2O cn phi k n cc cu t tn ti trong
h: H2O, H+, OH-, O2 v H2, Fe, Fe2+, Fe3+, HFeO2-, Fe(OH)2, Fe(OH)3 v cc phng trnh
phn ng c lin quan.
Bng III.2 ch ra nhng phn ng quan trng nht v cc phng trnh cn bng iu
kin:

15

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Gio trnh n mn & Bo v kim loi

Bng III.2

Hnh III.3: Gin E pH ca h Fe H2O ti 25oC.

c. ngha ca gin E pH
Gin E pH ca h kim loi nc (v d Fe H2O) c 3 vng c trng:
- Vng kim loi cn bng vi ion kim loi nng 10 -6 M. Theo quan im n mn
th vng ny c xem l vng an ton.
- Vng hydroxid kim loi (hay oxid kim loi) cn bng vi ion kim loi c nng
10-6 M. Vng ny thng kt ta dy c v c gi l vng th ng.
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BM CNHH i hc Nng Lm HCM

Gio trnh n mn & Bo v kim loi

Vng kim loi hay hydroxid kim loi (hay oxid kim loi) cn bng vi ion kim loi c
nng 10-6 M. Vng ny xy ra cc phn ng n mn v c gi l vng n
mn.
Trong mt gii hn no , gin E pH (M.Pourbaix) c a ra d on kh
nng n mn. Tuy nhin trn gin Pourbaix khng cho bit g v tc n mn v
bn cht bo v ca lp hydroxid hay oxid to thnh trong vng th ng.
V nguyn tc c 3 phng php chng n mn c rt ra t gin Pourbaix:
- in th in cc c th lm m hn so vi in th n mn v in th kim loi
nm trong vng an ton. Phng php ny gi l bo v catod (phn cc catod).
- in th in cc c th lm dng hn so vi in th n mn v in th kim
loi nm trong vng th ng. Phng php ny gi l bo v anod (phn cc anod).
- C th chuyn pH sang phi cho kim loi ri vo vng th ng, ngha l thay i
mi trng dn n ngng n mn.

II. C CH N MN IN HA
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 b mt gii hn hai pha: kim loi v dung dch cht in ly, khi kim
loi ha tan xy ra trn vng anod v km theo phn ng gii phng hydro hoc tiu th oxy
xy ra trn vng catod ng thi sinh ra dng in. Qu trnh n mn in ha xy ra tng
t nh s hot ng ca mt phin in b khp kn mch. (xem hnh III.4)

Hnh III.4: S n mn in ha ca kim loi trong dung dch in ly.

Trn b mt kim loi c tn ti cc vng anod v vng catod l do s chnh lch v th
trn b mt gii hn pha. C rt nhiu l do gii thch s chnh lch th ny. V d do c
mt ph gia hp kim, do s chnh lch mng cc tinh th kim loi.
gii thch qu trnh n mn in ha ca mt kim loi nhng trong dung dch in ly,
ta xt trng hp n gin c th hin trn hnh III.4. Trn b mt kim loi c hai vng:
vng anod v vng catod. Gi tr th in cc ti vng anod m hn so vi th in cc vng
catod. H ny c khp kn mch v xy ra cc phn ng sau:
Vng anod xy ra qu trnh oxi ha tc l kim loi b ha tan:
M Ze Mz+ (III.31)
17

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Gio trnh n mn & Bo v kim loi

Ion kim loi trn b mt in cc chuyn vo dung dch ng thi c cc electron d trn
b mt kim loi.
Cc electron d vng anod c dch chuyn n vng catod trn b mt kim loi v ti
xy ra cc phn ng km theo:
- Nu mi trng c ion H+ th xy ra phn ng gii phng hydro:
ZH+ + Ze (Z/2)H2 (III.32)
v khi s n mn km theo s gii phng hydro.
- Nu trong mi trng n mn c mt kh O2 v oxi th xy ra phn ng tiu th oxy:
(Z/4)O2 + Ze + ZH+ (Z/2)H2O (III.33)
Vy s n mn km theo s tiu th oxi c mt trong dung dch.
Qu trnh n mn ha tan kim loi cng nh qu trnh xy ra trn catod l gii phng
hydro hoc tiu th oxi thng bao gm cc giai on (xem hnh III.4 ) sau y:
Vng anod:
a) Giai on ha tan kim loi li electron trn in cc.
b) Giai on chuyn sn phm ca s oxi ha (chuyn cc ion t b mt kim loi vo th
tch dung dch)
Vng catod:
Trn catod v s gii phng hydro cng bao gm nhiu giai on sau:
a) Chuyn cc phn t tch in H 3O+ t trong th tch dung dch n lp dung dch phn
st b mt bng nhiu cch: hoc s khuch tn do chnh lch nng , hoc bng s
in di, hoc bng chuyn ng i lu.
b) Giai on kh lp v solvat ha ca phn t tch in H 3O+.
c) Giai on phng in ca ion H+: 2H+ + 2e H2
d) Giai on hp ph ca sn phm Hhp trn b mt in cc.
e) Chuyn sn phm vo dung dch v.v
Vy phn ng in ha xy ra trn b mt gii hn pha ca qu trnh n mn kim loi ti
vng catod cng nh anod bao gm rt nhiu giai on, song giai on no chm nht s
khng ch ng hc ca ton b qu trnh.
Ty thuc vo kh nng phn ng ngha l phn cc ca in cc s quyt nh giai
on khng ch ng hc. Trong in ha cng nh qu trnh n mn in ha, ng hc ca
qu trnh thng c khng ch bi hai giai on chm nht:
- S trao i electron ca cc phn t tch in trn b mt in cc xy ra chm nht
v khng ch ng hc trao i electron hoc cn gi l ng hc trao i in tch,
ng hc in ha.
- S chuyn vt cht t dung dch n b mt in cc xy ra ch yu do s khuch tn
l giai on chm nht trong qu trnh hoc n mn kim loi s l giai on khng ch
ng hc ca ton b qu trnh v thng gi l ng hc khuch tn.
III. NG HC CC QU TRNH IN CC
1. Hin tng phn cc v kh phn cc
a. Phn cc
Khi nhng hai thanh kim loi khc nhau vo mt dung dch in ly, chng to thnh hai
in cc khc nhau. Khi ni hai in cc vi nhau bng mt dy dn s c mt dng in
chy qua trong mch. in th in cc lc ny lch khi v tr cn bng. in th in cc
anod dch chuyn v pha dng. in th catod dch chuyn v pha m.
18

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Gio trnh n mn & Bo v kim loi

S dch chuyn in th ra khi trng thi cn bng gi l s phn cc.

b. ng cong phn cc
nghin cu qu trnh in cc, ngi ta thit lp quan h s ph thuc gia in th
in cc (E, V) vi mt dng in (I, mA/cm2).
Biu thit lp s ph thuc ca tr s in th in cc vo mt dng in ta gi
l ng cong phn cc.
Trn h ta , trc tung ca ta ghi tr s m ca in th, trc honh ghi tr s mt
dng in.
dc ca ng cong phn cc cng ln phn cc cng kn, ngc li dc ca
ng cong phn cc cng nh th phn cc cng nh, ngha l qu trnh in cc xy ra
d dng hn.
ng cong phn cc c ngha thc t gii thch nhng nh lut c bn ca qu
trnh n mn.
Xy dng ng cong phn cc bng thc nghim l mt trong nhng phng php c
bn nghin cu c cu ca qu trnh n mn.

th ng cong phn cc
ng cong phn cc c ngha thc t gii thch nhng nh lut c bn ca qu
trnh n mn.
Xy dng ng cong phn cc bng thc nghim l mt trong nhng phng php c
bn nghin cu c cu ca qu trnh n mn.
c. Phn cc
Nhng qu trnh lm gim s phn cc anod, catod c ngha l lm cho qu trnh anod v
catod tin hnh d dng hn gi l s kh phn cc anod, catod.
2. Phn cc anod
Qu trnh anod l qu trnh ha tan kim loi ngha l ion kim loi t mng li tinh th
kim loi chuyn vo dung dch v to thnh ion hydrat ha.
Mn+ . ne + mH2O Mn+.mH2O + ne
S phn cc anod lm cho qu trnh anod tin hnh kh khn hn. in th anod chuyn
v pha dng hn.
Nguyn nhn ca s phn cc anod l:
Do phn cc in ha hc c gi l qu th ion ha kim loi.
Lm chm s khuch tn ion kim loi t b mt vo dung dch.
19

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Gio trnh n mn & Bo v kim loi

To thnh mng th ng trn anod: trong dung dch in ly c cht oxi ha, khng c
cc anion hot ng nn n c kh nng to mng bo v lm cho in th anod
chuyn v pha dng hn.
3. Phn cc catod
Qu trnh catod l qu trnh kh ngha l qu trnh ly in t d do cc cht kh no .
K hiu l Xn+ + ne X
V d:
Cc ion b kh: H+.H2O + e H2 + H2O
Cc phn t trung tnh: O2 + 4e + 2H2O 4OH Mng khng tan: CuO + 2e + H2O Cu + 2OH Cc hp cht hu c: RO + 2e + 4H+ RH2 + H2O (R: gc ca phn t hu c).
Nguyn nhn ca phn cc catod:
Lm chm qu trnh catod do phn cc in ha gi l qu th phn ng phn cc catod.
Khuch tn cht kh phn cc t dung dch n b mt catod chm.
Khuch tn sn phm catod t b mt pha kim loi dung dch ra dung dch chm
IV.CC NHN T NH HNG N QU TRNH N MN IN HA
1. Cc nhn t bn trong
a. bn nhit ng ca kim loi
Kim loi b n mn in ha khi n ng vai tr in cc anod trong pin.
V phng din nhit ng, qu trnh n mn c kh nng t xy ra khi bin thin nng
lng t do ca n G < 0 hoc sc in ng ca cp nguyn t n mn Ed > 0. in th
in cc ph thuc vo bn cht ca kim loi .
b. Cu to v tnh cht ca hp kim
Hp kim c dng nhiu trong k thut. bn ca n ph thuc vo thnh phn v
cu trc ca n, c hai loi hp kim: hp kim 1 pha v hp kim nhiu pha.
Hp kim 1 pha l dung dch rn c s dng nhiu trong k thut n mn. Hp kim
nhiu pha c to thnh do cc kim loi cc trng thi kt tinh khc nhau. Quan im in
ha hp kim nhiu pha bn n mn km.
c. Trng thi b mt kim loi
B mt kim loi ng nht nhn bng kim loi bn hp.
B mt x x, khng ng nht d b n mn hn.
2. Cc nhn t bn ngoi
a. pH ca dung dch
pH = -log aH+
pH < 7: Mi trng acid.
pH = 7: Mi trng trung tnh.
pH > 7: Mi trng baz.
+ nh hng trc tip trong trng hp ion H+ hoc OH- trc tip tham gia phn ng
in cc lm thay i th in cc.
+ nh hng gin tip: to mng sn phm th ng lm gim tc n mn hoc ha
tan sn phm n mn lm mt kh nng bo v ca mng.
b. Thnh phn v nng cht in ly
Tc n mn in ha ph thuc vo bn cht dung dch mui ha tan v nng ca
n trong dung dch.
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BM CNHH i hc Nng Lm HCM

Gio trnh n mn & Bo v kim loi

Cc mui thy phn (v d Na2CO3) to mi trng kim lm thay i pH v nh

hng n tc n mn.
Cc mui ha tan tc dng vi kim loi to sn phm n mn kh ha tan.
Tc n mn cn ph thuc vo bn cht ca cation v anion ca dung dch mui ha
tan. Nu s hp ph ca cation hoc anion lm thay i c cu ca lp in tch kp gn
in tch in cc kim loi do lm gim tc n mn. Ngc li ph hy mng th ng
n s lm tng tc n mn.
c. Nhit v p sut mi trng
a s trng hp nhit gy nh hng n tc n mn. Nhit cng cao tc n
mn cng ln. Tuy nhin c mt s trng hp khi tng tc n mn n mt gi tr no
tc n mn li gim.
p sut cng nh hng n tc n mn. Thay i p sut lm thay i ho tan kh
trong dung dch, thay i qu trnh thy phn, do lm tng tc n mn.
d. Tc di chuyn ca dung dch in ly
nh hng ca tc di chuyn ca dung dch n tc n mn rt phc tp. C loi
khi tng tc ca dung dch th tc n mn tng nhng sau li gim hoc ngc li.
i vi mi trng c cc anion hot ng ph hy mng th ng, khi tng tc dng
chy th tc n mn tng ln.
e. nh hng ca dng in r
Dng in r l dng in t cc ngun khc nhau i vo lng t. Qu trnh n mn ch
yu do dng in 1 chiu sinh ra. Trong vng dng in i qua chia lm 3 vng nh:
- Vng catod l vng dng in tn i vo thit b. Vng ny khng b n mn.
- Vng trung ha l vng khng c dng in i vo v kiim loi khng b n mn.
- Vng anod l vng m dng in t thit b i vo t tr v ngun, vng ny kim
loi b n mn.
f. nh hng ca cu to thit b
Cu to thit b khng hp l c th gy ra vng ng sut nn gy n mn mnh, gy
ng cht lng n mn.
V vy, kt cu thit b hp l l mt trong nhng bin php chng n mn hiu qu.
V. XC NH TC N MN IN HA THEO IU KIN N MN
Phng php xc nh tc n mn in ha theo biu cn gi l phng php in
ha:
Tr s khi lng kim loi b n mn anod c xc nh theo nh lut Faraday:
m

A
A
q
It
nF
nF

Trong : m: khi lng kim loi b n mn (g)

A: nguyn t khi ca kim loi (g)
q: in lng chy t anod sang catod (C)
I: cng dng in n mn.
t: thi gian n mn (s)
n: ha tr ca kim loi
F: hng s Faraday.
Tc n mn in ha tnh bng khi lng kim loi b n mn trn n v din tch
trong mt n v thi gian, c xc nh theo cng thc:
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BM CNHH i hc Nng Lm HCM

Km

Gio trnh n mn & Bo v kim loi

m
A I
A

i A (III.34)
S A t nF S A nF

Trong : SA: din tch in cc anod (m2, cm2)

IA: mt dng anod (A/m2, A/cm2).
Km: tc n mn kim loi (g/m2.s; g/cm2.s).

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BM CNHH i hc Nng Lm HCM

Gio trnh n mn & Bo v kim loi

Chng IV: N MN TRONG CC MI TRNG

I. N MN TRONG MI TRNG KH
1. C ch n mn trong kh quyn
n mn trong kh quyn xy ra theo c hai c ch: n mn ha hc v n mn in ha.
n mn ha hc: l phn ng gia kim loi vi cc kh c tnh oxi ha trong mi
trng xung quanh nhit cao.
C ch: l phn ng oxi ha kh din ra ti b mt kim loi l ni tip xc trc tip ca
hai tc cht, bin kim loi thnh oxit, lm thay i tnh cht ha l ca kim loi hay hp
kim.
n mn in ha: l dng n mn xy ra trong mi trng khng kh t nhin c cha
nc ma hoc nhng ni ng nc.
C ch n mn in ha:
Ly c ch n mn in ha ca st trong kh quyn lm minh ha ( do st l vt liu kim
loi c dng nhiu lm thit b, my mc, cng trnh, nh xng)
Khi phi ngoi khng kh, st hoc thp s to thnh mt mng oxit rt mng bao gm
lp bn ngoi l oxit st t Fe3O4 (FeO.Fe2O3), bn ngoi l lp g FeOOH. Fe trong oxit st
t c th dng Fe2+ (FeO) hoc Fe3+ (Fe2O3). Cc vt nt trn lp g FeOOH cho php oxy
t kh quyn d dng xm nhp v oxi ha hon ton oxit st t thnh dng hydrat
Fe2O3.H2O hoc FeOOH (Fe2O3.H2O = 2FeOOH). Cc l xp trong oxit st t c lm y
bng nc ngng t v sn phm n mn khng tan. Do lp oxit st t s c tnh bo v
trong mi trng hi nc khng nhim.
Khng kh xung quanh thng cha mt lng SO2, cht ny phn ng vi nc v oxy
ha tan to H2SO4 trong cc l xp, dn n phn ng hon tan mt phn mng oxit to
thnh FeSO4. Mui ny b thy phn s cung cp thm mi trng axit, lm cho mng oxit d
ha tan hn, m rng l xp trong oxit st t v cho php dung dch in ly thm nhp d
dng vo b mt kim loi nn. Ngoi ra FeSO4 cn l cht ht m, s hp thu nc t kh
quyn v lm tng tc n mn khi m ln hn m ti hn.
Phn ng anod ha tan st xy ra di lp oxit st t Fe3O4
Fe Fe2+ + 2e
Ion Fe2+ trong dung dch bo ha (hoc gn nh bo ha) nm trong cc l xp ca Fe3O4
s phn ng vi oxy pha ngoi lp Fe3O4 to thm Fe3O4
3Fe3+ + 2OH- +1/2O2 Fe3O4 + H2O
Phn ng kh catod l
8FeOOH + Fe2+ +2e 3Fe3O4 + 4H2O.
trong Fe3+ trong g FeOOH b kh thnh Fe2+ trong Fe3O4 b mt tip xc hai pha.
Oxy kh quyn xm nhp ngang qua cc vt nt trong lp g c th oxi ha Fe 3O4 tr li
thnh g FeOOH.
3Fe3O4 + 0,75O2 + 4,5H2O FeOOH.

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