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 2.
N MN HA HC

CHNG
2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.1. nh ngha n mn ha hc
n mn ha hc l dng n mn xy ra trong mi
trng khng dn in, ph hy kim loi bng
phn ng ha hc d pha
C th chia lm 2 loi:

- n mn kh: tng tc ca kh v kim loi

nhit cao
- n mn kim loi ca cc cht lng khng dn

in (xng, du ha,)
3

CHNG
2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.2. c im qu trnh n mn ha hc cc kim loi

Khng xut hin dng in

Qu trnh oxy ha v kh xy ra ti mt v tr, mt
giai on

Sn phm n mn to thnh trc tip trong vng

phn ng trn giao din kim loi mi trng kh

CHNG
2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.3. C ch n mn ha hc kim loi nhit cao

nhit cao, phn ng oxy ha kim loi M xy
ra nh sau:
xM + y O2 MxOy

(1)

xM + yH2O MxOy+ yH2

(2)

H2 lm gin thp
Hin tng gin hydro (hydrogen embrittlement)
xM + yCO2 MxOy+ yCO

(3)

xM + yCO MxOy+ yC

(4)
Carbon to ra carbide5

CHNG
2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.3. C ch n mn ha hc kim loi nhit cao

Phn ng ha hc

aA + bB cC + dD
G = (ha th ca sn phm ha th ca tc cht)
= cC + dD (aA + bB)
Vi i l ha th

CHNG
2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.3. C ch n mn ha hc kim loi nhit cao

Ha th c tnh bng cng thc

= o + RTlnM
Vi
o l ha th chun
R: hng s kh l tng
T: nhit , K
M c th l h s hot hay hot ca cht
7

CHNG
2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.3. C ch n mn ha hc kim loi nhit cao

trng thi cn bng G = 0, ngha l:
coC + doD (aoA + boB) + RT(clnMC + dlnMD)
RT(alnMA + blnMB) = 0

Hay

oi = - RTlnK

Vi

MC MD

K
a
b
MA MB
c

CHNG
2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.3. C ch n mn ha hc kim loi nhit cao

Nng lng t do Gibbs tiu chun:
oi = Go
Nn
Go = -RTlnK

MC MD
c

MA MB
a

Phn ng t xy ra theo chiu t tri sang phi khi Go <0

9

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2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.3. C ch n mn ha hc kim loi nhit cao

Mt ct mu Cu sau khi oxy ha

Gin pha ngng t h Cu-O

Nu hp th oxy v cc phn ng xy ra trn b mt phn chia CuO/Cu2O

v Cu2O/Cu u cn bng m qu trnh n mn vn xy ra th khuch tn
s quyt nh ng hc ca qu trnh oxy ha
phng trnh ng hc biu din di dng ng parabol
10

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2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.3. C ch n mn ha hc kim loi nhit cao

Mt ct mu Fe sau khi oxy ha

Gin pha ngng t h Fe-O

11

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2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.3. C ch n mn ha hc kim loi nhit cao

Gin Ellingham ca mt s oxide
Gin Ellingham cho bit bn
nhit ng tng i ca mt oxide
trng thi tiu chun (pO2= 1at).
xM + y O2 MxOy
Go = Ho - T. So
Cng xung di gin th Go
ca phn ng to thnh oxide cng
m, mng oxide cng bn.
Go = RTlnpy/2oxy(cb)
G = Go RTlnpy/2oxy
Vi: G - thay i nng lng t
do, cal/mol;
Go- thay i nng lng t
do tiu chun (khi Poxy = 1at)
12

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2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.3. C ch n mn ha hc kim loi nhit cao

Go = Ho +T. So nn gin Go T gn nh l ng thng
trong : Ho Enthalpy (Nhit to thnh ca phn ng)
So Entropy, c trng cho mc hn lon ca h
GO2/MO =RTlnPO2/MO
trong : GO2/MO: thay i nng lng t do pO2/MO: p sut oxy
cn bng
Hng s kh R= 8,314 Jmol1K1
T- Nhit tuyt i, K
Poxy p sut oxy ring phn ban u ca mi trng, at
Poxy(cb) p sut oxy ring phn trng thi cn bng, c
trng cho s phn ly oxide.
Tng qut: Phn ng oxy ha kim loi c th xy ra khi G <0;
tc l khi Poxy > Poxy(cb)
13

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2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.3. C ch n mn ha hc kim loi nhit cao

V d: 850oC, Paladi (Pd) c b oxy ha trong khng kh
hoc trong kh oxy khng?
Bit rng, p sut phn ly oxide PdO nhit ny l 500
mmHg; Poxy khng kh = 0,21 at; Poxy = 1 at.
Gii:
PdO = Pd +O2
(Pcb= 500/760 = 0,658 at).
Pd khng b oxy ha trong khng kh, v Poxy khng kh < Pcb
Pd b oxy ha trong kh oxy nguyn cht, v Poxy > Pcb
14

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2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.3. C ch n mn ha hc kim loi nhit cao

V d: Xt kh nng oxy ha ca Ag 26,8oC (300K) v
126,8oC (400K)
Bit rng, p sut phn ly oxide Ag2O nhit 300K l
8,4.10-5 at; 400K l 0,69 at; poxy khng kh = 0,21 at
Gii:
Bc oxy ha theo phn ng:
4Ag +O2 = 2Ag2O
Ag b oxy ha trong khng kh 300K, v Poxy khng kh > Pcb
Ag khng b oxy ha trong khng 400K, v Poxy< Pcb
15

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2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.4. Cu trc lp oxide

oxide kim loi to thnh thng khng theo h s
t lng

oxide thng thiu hoc d kim loi

16

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2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.4. Cu trc lp oxide

Oxide thiu kim loi
- Cu trc MO cha l trng cation M2+: l trng cation

tch in dng oxide thiu kim loi l bn dn

loi p
- Trong oxide thiu kim loi MO, c mt tp cht kim
loi ha tr I
V d: Nu a Li+ (kch thc nh hn M2+) vo mt

phn l trng trong cation, mt l trng gim, ko

theo s khuch tn cation M2+ gim
17

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2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.4. Cu trc lp oxide

- Ngoi ra, tp cht kim loi ha tr III cng c mt
trong oxide thiu kim loi MO
V d: Cr3+ c kch thc ln hn M2+, Cr3+ khng th

chui vo cc l trng ca cation M2+, m phi nm nt

mng ca mng oxide MO. Nhm trung ha in tch,
Cr3+ ly in t t nguyn t M ln cn, to thm l

trng mi, tng s khuch tn cation trong MO

18

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2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.4. Cu trc lp oxide

Oxide d kim loi
- Nu kch thc cation nh, v d Zn2+ trong ZnO,

th cation d Zn2+ c th xen vo l trng trong mng

oxide. Hai electron lin kt vi Zn2+ mt cch khng
cht ch nn d di chuyn trong phm vi xung quanh
- Nu kch thc cation qua ln, v d Zr4+ trong ZrO2,
cation d nm nt mng, to mt l trng O2-, 4

in t d cng di chuyn tng i d dng trong

phm vi xung quanh
19

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2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.4. Cu trc lp oxide

- Tm li, ht ti in c bn l in t tch in m,
oxide d kim loi thuc bn dn loi n

- Thm vo MO cc cation ha tr I, s lm tng nng

cation xen k hay l trng anion, tng s khuch
tn anion O2-

- Ngc li, nu thm vo MO cation ha tr cao (ha

tr III), s khuch tn anion O2- gim
20

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2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.6. Quy tc Pilling - Bedworth

L t s gia mng oxide to thnh v th tch kim
loi tiu hao. c tnh theo cng thc:

PB=Voxide/Vkimloi=(Woxide.Dkimloi)/ (n. Wkimloi.Doxide)

Trong :
n S nguyn t kim loi trong 1 phn t oxide
Woxide Khi lng phn t oxide
Doxide Khi lng ring oxide
Wkim loi Khi lng nguyn t kim loi

Dkim loi Khi lng ring kim loi

21

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2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.6. Quy tc Pilling - Bedworth

c xy dng da trn gi thit O2 khuch tn qua
mng oxide n b mt kim loi.
Khng p dng PB i vi trng hp oxide to thnh

trn b mt oxide kh
Pilling Bedworth a ra quy tc:
PB = 1 2: mng oxide lin tc, bo v c kim loi
PB < 1: mng oxide mng, khng lin tc; khng bo v
c kim loi
PB >> 2: mng oxide tch khi b mt, khng bo v
c kim loi
22

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2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.6. Quy tc Pilling - Bedworth

Zn
Ca
Mg
Al
Pb
Pt
Zr
HF
Ni
Fe

ZnO
CaO
MgO
Al2O3
PbO
PtO
ZrO2
HfO2
NiO
FeO

1,58
0,64
0,81
1,28
1,28
1,56
1,56
1,62
1,65
1,7

T s Pilling-Bedworth
Ti
Cr
Fe
Fe
Si
Ta
V

TiO2
Cr2O3
Fe3O4
Fe2O3
SiO2
Ta2O5
V2O5

1,73
2,07
2,10
2,14
2,15
2,47
3,25
23

CHNG
2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.6. Quy tc Pilling - Bedworth

V d: Cho bit Mg c kh nng to mng oxide lin tc
khng? Bit khi lng ring ca Mg v MgO tng
ng l 1,74 g/cm3 v 3,58 g/cm3; nguyn t gam ca
Mg l 24,32 g.
Gii: S dng t s Pilling - Bedworth:

Voxide/Vkim loi = [(Woxide.Dkim loi )/ (n. Wkim loi .Doxide)]

VMgO/VMg = [(WMgO.DMg )/ (n. WMg .DMgO)].
VMgO/VMg = [(24,32 + 16).1,74]/(1 . 24,32 . 3,58) = 0,81.
V 0,81 < 1 nn mng MgO l mng oxide khng lin
tc.

24

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2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.7. Quy lut pht trin mng oxide

ng thng:

h = k1.t + C1
Vi h chiu dy mng oxide, k1 h s gc, t thi
gian tc dng ca mi trng

- Khi t = 0 C1 = h, c ngha C1 l chiu dy lp oxide

trc khi th nghim. Thng C1 ~ 0. h = k1.t
p dng i vi kim loi kim, kim th, oxide cc kim

loi thng hoa mt phn nhit cao (W, Mo)

mng thng xp, O2 d dng xm nhp b mt kim
loi to oxide.

25

CHNG
2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.7. Quy lut pht trin mng oxide

Oxi ha Mg cc
nhit khc nhau
k1 = tg

26

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2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.7. Quy lut pht trin mng oxide

ng parabol: h = k2.tb hoc h2 = k2t + C2

(C2 ~ 0)

p dng i vi
phn ln kim loi

(Fe,
mng

Ni,

Cu,),

thng

st

cht, c tnh bo v.
Vi b c trng
cho tnh bo v

ca mng oxide

27

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2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.7. Quy lut pht trin mng oxide

C ch:
- Kim loi phn tch thnh ion + e, v d:
M M2+ + 2e

- Mn+ v e chuyn vo lp oxide MO

- Oxi chuyn n giao din mng oxide v kh
- Oxi hp ph trn b mt mng oxide:
MO + O2 MO + Ohp
- Cc e ion ha oxi hp ph: Ohp + 2e O2- Chuyn O2- vo lp oxide
- Phn ng cation kim loi vi O2-: M + O2- MO
28

CHNG
2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.7. Quy lut pht trin mng oxide

ng logarit: h = k3.lgt + C

vi k3, C: hng s

p dng i vi s

trin

pht

mng

oxide nhit thp

(Cu

nhit

100oC, thp cacbon

nhit

400oC,

nhm

400oC)
29

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2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.7. Quy lut pht trin mng oxide

C ch:
- Khi chiu dy mng tng, lp ngoi st cht hn, ngn
cn s khuch tn ca mi trng qua mng lm mng
pht trin chm hn so vi quy lut parabol.

- Trong mt s trng hp, mng oxide c l xp rt nh

lm cho vic dn e v ion qua mng kh khn mng
pht trin theo quy lut logarit.

30

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2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.8. n mn ha hc kim loi trong cht lng khng in ly

Cht lng khng in ly l cc cht khng phn ly
thnh cc ion t do trong dung dch hoc trong trng
thi nng chy. V d:
Brom lng, lu hunh nng chy

Dung mi hu c (benzen, chloroform)

Phn ln cc cht lng khng in ly tr vi Fe v

hp kim ca Fe. Hydrocarbide dn xut halogen,

mercaptan, hp cht cha S c th phn ng vi Cu.
31

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2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.8. n mn ha hc kim loi trong cht lng khng in ly

Mt s cht lng khng in ly nh S (nng chy) hay
Br2 lng c th gy n mn theo cc phn ng sau:
2Fe + 3S (nng chy) Fe2S3
2Fe + 3Br2 (lng) 2FeBr3

Cc amin (R-NH2, R2-NH, R3-N) rt nguy him vi Cu v

hp kim Cu, c bit l R3-N; trong khi R-NH2 khng gy
n mn.

Cc loi hydrocarbide dn xut halogen phn ng vi

Mg, Zn, Sn, Al, Ag to thnh hp cht c kim.

32

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2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.8. n mn ha hc kim loi trong cht lng khng in ly

Hp cht S dng R-SH phn ng vi Cu to thnh
thioeter (mercaptite).
Cc alcohol v acide carboxylic dng R-COOH phn ng

vi kim loi to thnh alcolate v mui.

Cc acide bo phn t lng cao (acide stearic) phn
ng vi kim loi to thnh mui:
R-COOH + M RCOOM + 1/2H2
V d: acide adipic COOH.(CH2)4.COOH n mn

thp CrNi 0,40 g/m2.h, n mn Cu 0,64 g/m2.h

thot kh cha hydro.

33

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2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.8. n mn ha hc kim loi trong cht lng khng in ly

Cc dung mi hu c (aceton, benzen, toluen, xylen),
hydrocarbon lng (CnH2n+2 vi carbon t C5 n C15),
khng gy ra n mn kim loi nu khng cha tp cht,

bao gm c cc hydrocarbon khng no.

Cc k nguy him nu cha S hoc hp cht S
V d:
Khi du m cha 1,3% hp cht sulfide n mn
thp 0,038 g/m2.h, nhm 0,005 g/m2.h

Khi cha 3,2% sulfide n mn thp 0,055 g/m2.h,

nhm 0,012

g/m2.h

34

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2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.9. Chng n mn ha hc
Chng n mn kh:
- To hp kim chu nhit cao: thp cha Cr, Ni hm
lng cao (cc siu hp kim superalloy).

- Bao ph bo v: thm Al, Si, hn p, bc kim loi, phun

kim loi, m kim loi, trng men
- Kh bo v: v d nung thp trong mi trng CO+CO2
- Gim tc oxi ha: nung trong mi trng thiu khng
kh, to mng bo v oxide, chn mi trng nung thch

hp, a ph gia vo nhin liu

35

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2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

Siu hp kim UCSX-8 c

thnh phn: 6.4Co-1.8Cr3.6Mo-4.1W-5.2Re-2.1Ru6.8Al-10.0Ta-Ni (bal.)
(wt%), c c n tinh
th, 20 gi ti 1355oC
trong mi trng kh Ar bo
v chng b oxi ha.
M Pt 8 m v Pt 2 m
/Pt20Ir 6 m hoc phun ph
hp kim Pt, Pt/Ir vi hm
lng Ir =20% v 30%wt.

Thay i khi lng mu, mg/cm2

V D V PH HP KIM CHU NHIT CHO TURBIN KH

Phun ph Pt
Phun ph Pt20Ir
Phun ph Pt30Ir
M Pt
M Pt20Ir

Theo o Ch Tu et al. Journal Science & Technology, 2015, 53 (1B): 497-508.

36

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2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.9. Chng n mn ha hc
Chng n mn trong dung dch khng in ly
- Chn hp kim bn trong dung khng in ly.
V d: hp kim Al, cc loi thp khng g bn trong
xng cracking.
- Bao ph bo v.

V d: Thay v dung thp hp kim t tin c th

dng thp carbon thng thng v bc kim loi chu
mi trng n mn (phun Al), dung cc loi sn chu

du, cao su chu du

37

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2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.10. Hin tng gin hydro ca thp

Gin hydro c tc hi nghim trng n thp nhit
cao (t 200oC tr ln) v p sut cao (10-30 MPa). V

d nh trong cc thit b tng hp ammoniac (400-500oC,

15-25 MPa), hydro ha trong sn xut du m
Nguyn nhn gin:

i.

nhit cao, hydro ha tan vo thp to dung

dch rn vi Fe c gin ln.

ii. Khi nhit h xung, hydro c th thot ra ph

v lin kt trong tinh th gim bn.
38

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2. Nnim
MNv
HA
1.1. Khi
n HC
mn kim loi
Trng i hc Bch Khoa i hc Quc gia TP. HCM

2.10. Hin tng gin hydro ca thp

iii. Hydro xm nhp, tham gia phn ng hon nguyn
vi cementite Fe3C gim C trong thp:
Fe3C + 2H2 3Fe + CH4
ng thi, kh CH4 thot ra ph hy lin kt kim loi.
iv. Hydro hon nguyn FeO hnh thnh t trc bin
ht, to hi nc thot ra ph hy lin kt kim loi:
FeO + H2 Fe + H2O
Gii php:
Chn hp kim thch hp.
Nu do nguyn nhn i : Nung nng trong chn khng
hydro thot ra.
39