Chuong IV: Phan B Su dien phan https://websrv1.ctu.edu.vn/coursewares/supham/dienhoa/ch4b.

htm

PHN B : S IN PHN

I. NH LUT FARADAY
II. KHI NIM V S IN PHN - S PHN CC
1. Th phn hu
2. Th phn cc
III. N MN KIM LOI - HP KIM
1. S n mn ca kim loi nguyn cht
2. S n mn kim loi khng nguyn cht ( n mn in ha )
3. Cc yu t nh hng n s n mn in ha
4. Cc phng php bo v kim loi chng n mn

S in phn l qu trnh bin i ha nng thnh in nng tim tng trong cc cht thu c sau
phn ng di tc dng ca dng in . Nh vy nu phn ng oxi ha c th dng lm ngun in th phi
c mi quan h ngc li khi hiu th t vo cht s gy ra phn ng oxi ha kh trong n gi l s in
phn .
I. NH LUT FARADAY :
Trong pin in dng in pht sinh l nh cc phn ng ha hc xy ra trn b mt in cc nghi
l ha nng bin thnh in nng , ngc li khi in nng bin thnh ha nng nu ta cho dng in mt
chiu chy qua dung dch din phn hoc cht in phn nng chy th s c phn ng xy ra trn in cc .
Hin tng ny gi l s in phn .
Th d : in phn dung dch CuCl2 ta thu c Cu catod & Clor anod .
in phn dung dch NaOH ta thu c H2 catod & O2 anod .
in phn NaCl( nc)ta thu c Na catod & Clor anod .
S lin h gia lng in i qua v lng cht bin i in cc cho bi nh lut Faraday :
Khi lng cht tham gia phn ng in cc t l vi in lng i qua v ng lng in ha ca cht
.

Ta c phng trnh : m = = keq

q = It : in lng ; nu I Am , t s q = 1 coulomb
I Am , t gi q = 96500 coulomb
q = 26,8 am. gi

: ng lng ca cht tham gia phn ng ( hoc ca sn phm )

ke = : ng lng in ha
ng lng in ha ca mt cht c th khc nhau n ty thuc vo phn ng in cc .

Fe - 3 Fe3+ ng lng in ha : = 18 g/F

Fe - 2 Fe2+ ng lng in ha : = 28 g/F

Fe2+ - Fe3+ ng lng in ha : = 56 g/F

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Khi m = th q = F : in lng cn thit phng thch 1 ha tr gam tc 1 ng lng gam

= ng lng in ha ca sn phm .
l 1Faraday tc l in lng tng ng vi 1 mol sn phm
F = Noe
= 6,023.1023 e. mol-1. 1,062.10- 19coul.e-1

= 96488 coul.mol- 1 # 96500 coul. mol - 1

Th d : Nu cho in lng q = 1 coulomb i qua cc dung dch AgNO3,CuSO4 , H2SO4 th trn
catod ta s thu c 1,118mg Ag ; 0,329 mg : v 0,01044 mg H2 . nhng i lng ny chnh l ng
lng in ha v chng t l vi ng lng ha hc . V :

m=

Vi Ag = 107,87 ( 107,87 ) . 1 = 0,001118 F = # 96500coul.

Vi Cu = 63,54 ( ) .1 = 0,329 .10-3 F = # 96500 coul.

Vi H = 1,0079 = 0,01044 F = # 96500coul.

Vy gii phng hoc chuyn ha 1 ng lung gam bt k cht in phn th cn 1 in lng
nh nhau v bng 96500 coulomb .
l nh lut Faraday th 2 :
Khi cho cng mt in lng i qua cc cht in phn khc nhau th lng cht b chyun ha s
t l vi ng lng in ha m khng ty thuc vo bn cht v kch thc ca bnh in phn v ca
cc in cc .

II / KHI NIM V S IN PHN - S PHN CC : TOP

Kho st nhng qu trnh xy ra ranh gi pha in cc - dung dch thng l trng thi cn
bng thun nghch ng vi trng hp khng c s lu thng dng in trong h in ha . Tuy nhin trong
nhiu trng hp trong h in ha c s lu thng dng in vi cng xc nh.
S xut hin ca dng in ny l do :
- S ng mch ca pin in ha .
- Hoc h in ha l mt bnh in phn c 2 in cc c nhng vo dung dch in phn
c ni vi ngun in bn ngoi gy ra cc phn ng in ha . l s in phn .
Khi h lm vic trong iu kin khng cn bng ( khng thun nghch ) th hiu th V o c 2
u in cc khc vi sc in ng E trng thi cn bng .
- Nu l pin in ha th V< E
- Nu l bnh in phn th V > E
Trong c hai trng hp trong mch in ha u c s lu thng dng in .
l nguyn nhn gy ra s chnh lch VE . Hin tng ny gi l s phn cc .
Th d 1 : in phn dung dch HCl long vi 2 in cc Pt

Khi cc ion H+ , Cl - b phng in trn in cc n s to ra lp kh hp ph trn b mt thanh Pt

. Do thay v l 2 in cc Pt th by gi n tr thnh 2 in cc kh : in cc kh hydro H +/ H2 / Pt
in cc kh Clor Cl - / Cl2 / Pt
2 in cc ny to thnh 1 pin : Pt/ H2 / H+ , Cl - / Cl2 / Pt

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catod : 1/2 Cl2 + Cl -

anod : 1/2 H2 - H+
Phn ng ca pin 1/2 H2 +1/2 Cl2 H + + Cl -
Nu Eo = 1,3583 volt
HCl ( 1N ) & = 0,82
Ta c E = Eo - 0,0591 log a+.a-
= 1,3583 - 0,0591 log ( 1 . 0,82 )2
= 1,3685 volt
Vy mun in phn dung dch HCl ( 1N ) ta phi p vo bnh in phn 1 in th ti thiu l 1,
3685 volt . l th phn cc Ep .
Trong thc t s in phn dung dch HCl cn phi c mt in th ln hn th s in phn mi
xy ra c . l th phn hy Eh vi E h > Ep .
Th d 2 : in phn dung dch H2SO4

hnh thnh pin : Pt/H2 /H+ , OH _ / O2 / Pt

* H+
1/4O2 + 1/2 H2O + OH -

phn ng ca pin :1/2H2 + 1/4O2 + 1/2 H2O H + + OH -

E = Eo - = 0,403 -
= 0,403 - 0,0591 ( - 14 ) = 1,23 volt
Thc nghim o Eh = 1,69 volt
Th d 3 : in phn dung dch AgNO3( 1 N)

= - = 0,3097
= 0,403- 0,0591 log ( 10- 7) = + 0,0591log
= 0,8167volt = 0,799 + 0,0591log0,3097
= 0,799 - 0,03
= 0,769volt
vy E pin = 0,8167 - 0,769 = 0,0477 volt
Thc nghim o E h = 2,2 - 2,3 volt
Thc t trong s in phn cc oxacid H2SO4, HNO3 , H3PO4 H2 ;O2 ( sn phm
)
vi in cc Pt c Ep = 1,23 volt & Eh = 1,78 volt
i vi cc baz NaOH ; KOH ; NH4OH H2 ; O2 ( sn phm )
vi in cc Pt c Ep = 1,23 volt & Eh = 1,78 volt
cn i vi mt s mui ZnSO4 ; CdSO4 c sn phm H2 ; O2
vi in cc Pt c Ep = 1,26 volt & Eh = 2,2 - 2,3 volt
Nh vy ta thy th phn hy cc dung dch oxacid , baz trong nc u bng 1,7 volt ln hn

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nhiu so vi sc in ng thun nghch tnh theo l thuyt

( 1,23 volt ) ngha l Eh khng ph thuc vo bn cht ca cc oxacid , baz , mui v thc cht s in phn
l nc b in phn v sn phm to thnh l kh H2 & O2 .Ngi ta gi hiu th gia in th ca in cc
khi c dng in v th cn bng l qu th .
K hiu:
= V - Ecb

=
=
= a - c
: in th ca in cc khi c dng in lu thng
: in th in cc cn bng
Hin tng qu th xut hin khi khuynh hng t ti cn bng gn in cc b chm tr c th
l do qu trnh nhng in t hay nhn in t ca cc ion trn b mt in cc .Ni chung qu th c gi
tr nh nhng phn ng ha tan hoc gii phng kim loi trn in cc , c th 1 volt khi c s thot kh
H2 hoc O2 trn in cc . Do qu th ca hydro cao khi in phn c th gii phng kim loi t dung dch
mc d in th chun ca chng thp hn nhiu so vi ion hydro .
V d : in phn dung dch ZnSO4 ( pt )
= - 0,76 volt
= 0
t gi tr in th chun ny ta d dng thy ion H+ s phng in trc v c kh H2 that ra trn catod .
Tuy nhin qu th Hydro so vi km khong 1 volt khin cho km li c gii phng trc trn catod , ion
H+ ch b phng in khi no nng km gim xung ti mc in th ca km tr nn cao hn qu th
Hydro . ln ca qu th ph thuc vo bn cht ca in cc , mt dng , thnh phn dung dch v
cc yu t khc .
1905 Tafel a ra phng trnh m t s ph thuc ca qu th vo mt dng :
= a + b log i

a : ph thuc vo bn cht in cc vi Pt th a = 0,3 V

vi Pb th a = 1,36 V
b : c trng ch yu cho qu trnh in ha v t ph thuc vo cht liu in cc .
i : mt dng

1/ Th phn hy : TOP

Khi kho st s in phn dung dch HCl vi in cc Pt , nu tng dn hiu th t vo 2

in cc ri theo di s thay i cng dng in ta c ng biu din I theo V c dng :

Thot u th dng in rt nh ch khi no

hiu th t c gi tr xc nh , khi I
tng vt ti l th phn hy Eh , lc cc
kh bt u thot ra trn in cc .

Ta nhn thy :
- ng biu din khng cn l ng thng theo nh lut Ohm I = V/R nh vt dn loi 1 .
- on AB ng vi V < Eh : trn nguyn tc khng c dng in i qua t bo nhng thc t vn
c dng in rt nh xut hin v sn phm sinh ra trong s in phn thay v bm vo in cc li khuch

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tn chm tr li dung dch , b p li c dng in nh i qua t bo ti to li vt cht mt .

- Ti M : V = Eh : cc kh bt u that ra trn in cc .
- on CD : dng in cung cp vo hon ton t l vi V .

2/ Th phn cc TOP
Phn cc l hin tng ng hc lm cho cc phn ng trong s in phn khng xy ra c th
cn bng m xy ra th ln hn . chnh lch in th gi l th phn cc .Ngi ta phn bit 2 dng
:

- Phn cc nng
- Phn cc hot

a/ Phn cc nng : l do ni s thay i nng cht in phn quanh cc in cc khin cho

t bo c th to ra sc in ng chng li V p vo t bn ngoi .
Th d : in phn dung dch AgNO3 vi in cc Ag
anod : Ag - Ag +
catod : Ag + + Ag
T phn ng trn ta thy nng Ag+ vng xung quanh catod gim cn nng Ag+ vng xung quanh
anod tng . S chnh lch nng tng ng vi s hnh thnh 1 pin nng chng li V ngoi .
Gi s ta c in cc ng vi phn ng in cc l : Ox + n Kh
Gi a l nng ban u ca cht in phn .
trng thi cn bng in th ca in cc l :

sau thi gian t nng ca cht in phn l a , khi in th ca in cc tng ng l :

Mc khc trong s in phn th nng ca dng oxi ha & dng kh ni in cc tip xc vi

dung dch s b thay i v qu trnh khuch tn ni in cc xy ra chm . chnh l nguyn nhn gy ra
s phn cc v cng dng in t l vi vn tc khuch tn .

vkt = SD vi : b dy lp in kp
D : thng s khuch tn : s mol cht khuch tn q ua mt n v din tch trong 1 n v thi gian ( hay cn
gi l h s khuch tn cm2s-1
S : din tch in cc

mc khc : v =

= ke I=

= ( khi c 1 F i qua dung dch cha 1 ng lng gam cht in phn )

Khi a' 0 th i imax = FD

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thay a'/a vo

vi = : qa th ng vi s phn cc nng gi l qa th nng

Khi = 0 th I = 0
cng ln th i imax

cng nh & <<

i t l vi , do dng in cng ln s phn cc cng mnh .

ng cong biu din s ph thuc mt dng vo th phn cc gi l ng cong phn cc .

Sc in ng cn bng Ecb = jc - ja = AB

jc : in th in cc catod lc cn bng : im B

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ja: in th in cc anod lc cn bng : im A

b/ Phn cc hot ha :
S khuch tn khng phi l nguyn nhn duy nht dn n s sai lch in th .
Th d : S kh H3O+ + 1/2 H2 + H2O
Khi H3O+ n cc m nhn in t , vic di chuyn ny xy ra rt nhanh ( v ion H+ c linh
rt ln ) do qu th ca H2 phi tht nh nhng thc t cho thy th in cc Hydro c th thay i
rt nhiu c khi > 1,5 volt .

S phng in ca ion H3O+ phi qua nhiu giai on :

ion H3O+ b lp solvat ha
ion H+ nhn in t tr thnh nguyn t H
Kt hp 2 nguyn t H thnh phn t H2
To bt kh tch khi dung dch
Trong cc giai on trn c th c mt giai on no xy ra vi tc chm hn cc giai on
khc . Ni cch khc giai on ny c Ea cao ( n i hi phi c thm nng lng ) . Chnh v th m hiu
th gia 2 in cc phi tng ln . Th in cc ny lch i so vi th cn bng . S phn cc gy nn bi s
chm tr ca qa trnh no khng phi l qa trnh khuch tn c gi l phn cc ha hc hay phn cc
hot ha , gi tr ca phn cc hot ha gi l qu th hot ha . K hiu (A. Phn cc hot ha thng rt
ln khi c s hnh thnh kh .

III. N MN KIM LOI - HP KIM :

n mn kim loi & hp kim l qu trnh t ph hy cu trc kim loi & hp kim di tc dng
ca mi trng xung quanh . Tu theo c ch ph hy ca kim loi & hp kim m ngi ta phn bit s n
mn ha hc , s n mn in ha v n mn sinh hc khi kim lai tip xc vi khng kh m ( n mn
trong kh quyn ) hoc tip xc vi t ( n mn trong t ) .

1/ S n mn ca kim loi nguyn cht :

TOP

Th d : Nhng mt thanh Zn nguyn cht vo dung dch ZnCl2 th khi cn bng in ha c

thit lp ta c :
Zn - 2 Zn2+
Da vo phng trnh Nernst ta c th tnh c
Nu bng cch no ta lm cho j ca Zn lch khi gi tr cn bng v pha m hn ( pha catod )
th xy ra s phng in:
Zn2+ + 2 Zn
Khi Zn c gii phng v bm vo b mt thanh Zn

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Tri li nu th in cc ca Zn b lch v pha dng hn ( pha anod ) th c hin tng ha tan

Zn vo dung dch .

Ti th s ha tan & s phng in ca Zn2+ xy ra vi tc bng nhau :

Nu thm HCl vo dung dch ZnCl2 :

v = - 0,763 volt < 0
= 0 do tnh oxi hoa cua H3O+ mnh hn Zn2+ nn H3O+ b kh trn b mt thanh Zn
H3O+ + 1/2 H2 + H2O
s tiu th trong phng trnh ny lm cho mt trn thanh km b gim i khin cho chuyn
dch v pha dng hn to thun li cho qu trnh ha tan Zn ng thi hn ch s gii phng H2 trn thanh
Zn .Khi s chuyn dch in th t ti tr s jD th tc gii phng H2 bng tc ion ha Zn .
jD : gi l th dng , ti :
s n mn trong HCl ngng li .
Kh H2 that ra lp oxid mng hnh thnh ph ln b mt kim loi nguyn cht bo v kim loi
khng b n mn tip tc . l s n mn kim loi vi s kh phn cc hydro vi iu kin jM(cb) < jH2
( cb ) . .

m = 0,0591logaH+ -

=- 0,0591pH -

Ga tr 25oC ng vi cc pH & PH2 :

pH

0 7 14
5.10 - 7 0,186 - 0,228 - 0,641
1 0 - 0,414 - 0,828

bng trn cho thy pH cng lncng m kim loi cng t b n mn .

Th d : Fe, Zn , trong dung dch HCl , H2SO4
Pb , Sn trong mi trng kiew62m
Mg , trong nc hay trong dung dch NaCl ( mi trng trung tnh )

Mt dng n mn khc kh ph bin trong thin nhin v rt quan trng . l s n mn c oxi

trong kh quyn ha tan vo mi trng n mn . l s kh phn cc oxi . Ty theo mi trng :

- Mi trng trung tnh hoc kim : O2 + 2 H2O + 4 4OH -

- Mi trng acid : O2 + 4 H+ + 4 2 H2O
iu kin kim loi b n mn vi s kh phn cc oxi l :

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Ga tr 25oC ng vi v pH :

pH

0 7 14
0,21 1,218 0,805 0,391
1 1,229 0,815 0,4

>0 , do s n mn vi s kh phn cc O2 ph bin hn so vi H2 v thng gp khi kim loi

tip xc vi khng kh , nc ngt , nc bin , t ...
Tm li : iu kin mt dng n mn no xy ra l :

: l in th cn bng ca cht kh phn cc ( H2 , O2).

2/ S n mn kim loi khng nguyn cht ( n mn in ha ) :

TOP

Trong thc t rt t gp kim loi hon ton tinh khit m mt mc no kim loi c ln
mt hay nhiu kim loi tp cht ngi ta gi kim loi b nhim cc tp cht l kim loi nhim .
Kim loi nhim b n mn vi tc ln hn nhiu.
Th d : Zn nhim 10% kim loi khc ( Cu ) trong mi trng H2SO4 ( long )
= 0,337 volt
= -0,763 volt
>

S chnh lch in th to ra 1 pin in ha gm 2 in cc bng kim loi vi bn cht khc nhau

nhng vo dung dch in phn :
Zn / H2SO4/ Cu
- anod : Zn - 2 Zn2+
in t chuyn t Zn sang Cu , th Zn b chuyn dch v pha anod ( - ) ng vi s ha tan thm ca Zn ng
thi km hm s gii phng kh H2 trn Zn , Cu nhn in t khin cho th ca Cu chuyn dch v pha
catod , ti catod :
2H+ + 2 H2
Kt qa l Zn c tip tc b n mn cho n ht .
Th d 2 : Fe ( ln Cu ) trong khng kh m : Fe / H2CO3 / Cu
= - 0,44 volt
= 0,337 volt

Cui cng b mt Fe c ph mt lp oxid st gm FeO , Fe2O3. chnh l lp g st lp ny

c cu to xp nn O2 ca khng kh tip xc c vi st bn trong lp g lm cho st tip tc b n mn .

3/ Cc yu t nh hng n s n mn in ha :

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C nhiu yu t nh hng n s n mn in ha :
* ( ca kim loi tp cht cng khc ( ca kim loi b n mn th tc
n mn cng ln .
Khng kh cng m cng n mn cng tng .
Nhit tng th tc n mn cng tng
xp ca lp sn phm cng ln th kim loi cng b n mn nhanh .

4/ Cc phng php bo v kim loi chng n mn : TOP

- Ph ln kim loi mt lp phi kim loi ( khng phi l kim loi ) hoc dng nhng cht hu c :
du m , parafin , vaselin ...trng men ... to ra trn mt kim loi mt mng mng che ch cho kim loi .
- Ph ln kim loi mt kim loi t b n mn : Zn , Sn , Ni , Cr ...thng ngi ta dng phng
php m xi
Th d : m Niken , dung dch in ly l NiSO4 v mt s cht khc , vt cn m lm catod , khi c dng
in i qua Ni2+ bm vo catod ( vt m ) do s phng in ca Ni2+ thnh Ni kim loi ph kn b mt vt
cn m .
- Thay i mi trng n mn : ch c th thc hin trong iu kin th tch hn ch .

BNG TR S IN TH OXI HA KH

in cc Phn ng in cc

Li+/ Li Li+ + e =Li -3,05

Rb+/ Rb Rb+ + e = Rb -2,93
Cs+/ Cs Cs+ + e = Cs -2,92
-2,92
K+/ K K+ + e = K
-2,90
Ba2+/ Ba Ba2+ + 2e = Ba
-2,76
Ca2+/ Ca Ca2+ + 2e = Ca -2,71
Na+/Na Na+ + e = Na -2,37
Mg2+/ Mg Mg2+ + 2e = Mg -1,66
Al3+/Al Al3+ + 3e = Al -1,63
Ti2+/Ti Ti2+ + 2e = Ti -1,18
Mn2+/Mn Mn2+ + 2e = Mn -0,92
Se2+/Se Se2+ + 2e = Se -0,763
-0,74
Zn2+/Zn Zn2+ + 2e = Zn
-0,44
Cr3+/Cr Cr3+ + 3e = Cr
-0,402
Fe2+/Fe Fe2+ + 2e = Fe -0,335
Cd2+/Cd Cd2+ + 2e = Cd -0,27
Tl+/Tl Tl+ + e = Tl -0,25
Co2+/Co Co2+ + 2e = Co -0,136
Ni2+/Ni Ni2+ + 2e = Ni -0,126
Sn2+/Sn Sn2+ + 2e = Sn 0,00
Pb2+/Pb Pb2+ + 2e = Pb 0,337
0,401
H+/H2/Pt 2H+ + 2e = H2
Cu2+/Cu Cu2+ + 2e = Cu 0,520
OH-/O2/Pt 0,536

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0,799
Cu+/Cu 0,854
I-/I2 Cu+ + e = Cu 1,359
1,5
Ag+/Ag I2 + 2e = 2 I-
Hg2+/Hg Ag+ + e = Ag
Cl-/Cl2,Pt Hg2+ + 2e = Hg
Au3+/Au Cl2 + 2e = 2Cl-
Au3+ + 3e = Au

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