1

Chng 3. Th in cc v sc in ng ca pin in Trnh Xun Sn

n mn v bo v kim loi. NXB i hc quc gia H Ni 2006. T kho: n mn v bo v kim loi, Th in cc, Sc in ng ca bin in, in cc,
Lp in kp, Sc in ng.

Ti liu trong Th vin in t H Khoa hc T nhin c th c s dng cho mc ch hc tp v nghin cu c nhn. Nghim cm mi hnh thc sao chp, in n phc v cc mc ch khc nu khng c s chp thun ca nh xut bn v tc gi.

Mc lc
Chng 3 Th in cc v sc in ng ca pin in .................................................. 2 3.1 in cc v nguyn nhn sinh ra th in cc........................................................ 2 3.2 Lp in kp trn b mt in cc.......................................................................... 2 3.3 S ph thuc ca gi tr th in cc vo nng cht phn ng .......................... 4 3.4 Phn loi in cc .................................................................................................. 6 3.4.1 in cc loi 1 ................................................................................................... 6 3.4.2 in cc loi 2 ................................................................................................... 7 3.4.3 in cc kh ..................................................................................................... 10 3.4.4 in cc oxi ho kh (Redox).......................................................................... 12 3.4.5 in cc oxit kim loi ...................................................................................... 12 3.5 S dng gi tr th in cc tiu chun xt chiu hng phn ng....................... 14 3.6 Pin in (Pin Ganvani hoc mch in ha)......................................................... 16 3.6.1 Pin in v cc phn ng xy ra trong pin ........................................................ 16 3.6.2 Sc in ng ca pin in............................................................................... 17 3.6.3 Phn loi pin in ............................................................................................. 18 3.7 Phng php o sc in ng v ng dng........................................................ 20

Chng 3 Th in cc v sc in ng ca pin in
3.1 in cc v nguyn nhn sinh ra th in cc
in cc l mt h in ha gm cht dn in loi 1 tip xc vi cht dn in loi 2. V d: Kim loi Cu tip xc vi dung dch mui sunfat ng Cu2+SO4/Cu hoc Cu2+/Cu hoc Zn2+/Zn; Fe3+,Fe2+/Pt vv (mt gii hn gia hai pha rn v lng c k hiu bng gch cho / hoc l gch thng). V mt ha hc tm phn ra in cc tr v khng tr. Mt in cc c gi l in cc tr nu dy dn loi 1 khng tham gia phn ng v ch c chc nng l trao i electron, v d in cc Pt trong cc h in phn dung dch NaOH, dung dch H2SO4 Ngc li, mt in cc gi l khng tr nu cht dn in loi 1 c tham gia phn ng oxi ho kh trn mt gii hn pha v sau mt thi gian lm vic khng cn nguyn vn nh lc ban u V d: Anot Ni trong cc qu trnh m in. in cc Ni b ha tan theo phn ng: Ni 2e Ni2+ Sau thi gian phn ng khi lng anot niken b gim i v b chuyn thnh ion Ni2+ i vo dung dch. Trn b mt gii hn ca hai pha cht dn in loi 1 v 2 lun tn ti lp in kp v n l nguyn nhn sinh ra th in cc

3.2 Lp in kp trn b mt in cc
Khi nhng mt kim loi Me vo trong dung dch mui cha ion Men+ ca n (v d nhng kim loi bc vo dung dch AgNO3 long, kim loi ng trong dung dch CuSO4) trn b mt gii hn xy ra hin tng chuyn ion kim loi t kim loi vo dung dch. Ta xt trng hp kim loi bc trong dung dch AgNO3 long (hnh 3.1).

Hnh 3.1 S hnh thnh lp in kp trn mt gii hn pha ca in cc Ag trong dung dch AgNO3 long

a) S di chuyn ca ion Ag+ (t kim loi) vo trong dung dch; b) Lp in kp trn b mt gii hn pha; c)S phn b th theo chiu dy lp in kp
+ Trn hnh 3.1a m t s dch chuyn ion Ag+ trn b mt kim loi ( Ag KL ) i vo dung + dch AgNO3, thot u ion Ag KL i vo dung dch vi tc ln v li electron trong kim + loi. V b mt kim loi Ag d in tch m nn ion Ag KL th 2 i vo dung dch kh khn hn, tip theo sau cc ion th 3, th 4 i vo trong dung dch cng kh khn hn na. Ngc li, theo thi gian nng ion Ag+ gn st b mt kim loi tng dn ln v lm d dng cho cho s dch chuyn ion Ag+ t dung dch i vo b mt kim loi. Sau mt thi gian + nht nh trn b mt gii hn pha t trng thi cn bng ca hai qu trnh ion Ag KL i vo dung dch v ion Ag+ t dung dch i vo trong kim loi. Khi h t trng thi cn bng, trn b mt gii hn hnh thnh lp in kp, vi hai bn tch in ngc du v chiu dy lp kp c bn knh nguyn t () (xem hnh 3.1c). Do c lp in kp sinh ra th in cc E, s phn b th in cc ca lp in kp trn mt gii hn pha theo chiu dy ca lp d l tuyn tnh (hnh 3.1c).

Lp in kp gi tt l lp kp trn hnh 3.1b cn gi l lp kp c - lp kp Helmholtz - lp kp ny ch yu l do lc tng tc tnh in v c p dng cho cc dung dch tng i m c Khi dung dch tng i long v tnh n s chuyn ng nhit cc ion gn b mt in cc, th s phn b th ca lp kp theo chiu dy lp kp gm 2 phn: phn tuyn tnh v phn khng tuyn tnh.

Hnh 3.2 a) Lp kp c tnh n chuyn ng nhit; b) S phn b th E(V) theo chiu dy lp kp

Trong trng hp ny Stern chia lp kp thnh 2 phn: + Phn Helmholtz - Cn gi l lp kp c (c k hiu l (*) trn hnh 3.2b). + Phn khuch tn - Phn Goui- Chapman (c k hiu (**) trn hnh 3.2b). Nghin cu v cu trc lp kp l mt vn rt hp dn cc nh in ha, v n c ngha khoa hc rt ln, song c nhng hn ch nht nh v lp kp rt phc tp. Vn ny c trnh by y hn trong cc gio trnh chuyn .

3.3 S ph thuc ca gi tr th in cc vo nng cht phn ng, phng trnh Nernst

Trn b mt gii hn pha cht dn in loi 1 v loi 2 ca in cc xy ra phn ng oxi ha kh dng: i Oxi + Ze Khi i = 1 ta c: Oxi + Ze
2+

i Redi Redi Cu

(3.1) (3.2) (3.3)

V d trn in cc Cu /Cu xy ra phn ng : Cu2+ + 2e Gia bin thin ha th phng trnh: ca phn ng (3.3) v th in cc E quan h vi nhau theo (3.4)

= AMax = Z.F.E trong : Z l s electron trao i; F l hng s Faraday (96493 C); AMax l cng cc i hu ch. p dng phng trnh (3.4) cho phn ng (3.3) ta c:

5
= C SP trong : C: Tng ha th ca cc cht u tham gia phn ng; SP: Tng ha th ca cc cht sn phm c to ra. Ta c: = Cu2 + + 2e Cu
o = Cu2 + + RTln aCu2 + + e Cu o = Cu2 + + 2e Cu + RTln aCu2 + = ZFE

(3.5)

Vy th in cc E bng: E=
o Cu2 + + 2e Cu

ZF
RT ZF lg aCu2 +

RT ZF

lg aCu2+

E = Eo + trong : E =
o o

(3.6)

o Cu2 + + 2e Cu

ZF

gi l th in cc tiu chun ( 25oC).

Vy: E = E khi hot aCu2 + = 1. Phng trnh (3.6) gi l phng trnh Nernst. Cn ch rng bng con ng l thuyt v thc nghim khng xc nh trc tip c gi tr tuyt i ca th in cc tiu chun Eo. Phng trnh Nernst vit cho phn ng tng qut (3.1) nh sau: E = Eo + hoc 25oC ta c: E = Eo +
0,059 Z lg
i a oxi i a Re di i a oxi i a Re di

RT ZF

ln

(3.7)

(3.8)

trong k hiu l tch s cc hot . V d vit phng trnh Nernst cho cc in cc sau: Zn2+/Zn vi phn ng in cc Zn2+ + 2e
EZn2 +

Zn 25oC:
2 lg aZn2 + a Zn

Zn

= Eo 2 + Zn

+
Zn

0,059

Fe3+, Fe2+/Pt vi phn ng in cc Fe 3+ + 1e

EFe3 +
o = EFe3 +

Fe2+ 25oC:
lg aFe3 + aFe2 +

+
Fe2 +

0,059 1

Fe2 +

O2(Pt)/H2O vi phn ng in cc O2 + 4e + 4H+

2H2O

25oC:

EO2

=
H2O

o EO2

+
H2O

0,059 4

lg

pO2 .a4 + H a 2 2O H

Thng thng hot kim loi tham gia phn ng c quy c bng n v (tr trng hp kim loi trong hn hng thy ngn), hoc hot ca nc bng n v. i vi cht kh thay cho vic biu din nng ngi ta dng khi nim p sut v d
PO2 , PH2 ...

T cc phng trnh (3.6), (3.7), (3.8) cho thy rng, mun xc nh gi tr th in cc E cn phi bit chnh xc nng cc cht tham gia phn ng v gi tr th in cc tiu chun Eo. Gi tr th in cc tiu chun Eo ca mt in cc bt k c xc nh da vo th in cc tiu chun hiro c gi tr chp nhn bng 0,00 V. V d th in cc tiu chun ca in cc km: Zn2+/ Zn c gi tr bng 0,76 V NHE, c ngha l n c so vi th ca hiro (v in cc hiro s c cp n trong phn sau) hoc vi in cc ng Cu2+/Cu c gi tr th tiu chun bng 0,34 V NHE; qua nhng v d ta c th nh ngha gi tr th in cc tiu chun Eo nh sau: "Gi tr th in cc tiu chun Eo ca mt in cc bt k cn xc nh l sc in ng E ca pin in gm in cc tiu chun hiro ( aH+ = 1 v PH2 = 1 atm) v in cc tiu chun ca in cc cn xc nh". Du ca gi tr th in cc tiu chun chp nhn l du dng so vi in cc tiu chun hiro nu trong pin in, in cc tiu chun cn xc nh l cc dng (catot) so vi in cc tiu chun hiro v ngc li. Trn c s o gi tr th in cc tiu chun ca cc in cc ngi ta xp cc gi tr th in cc tiu chun thnh bng (xem bng 3.1) gi l bng gi tr th in cc tiu chun. Nng cc cht phn ng ca in cc thng c biu din qua i lng hot a ca cc ion tham gia phn ng, trong trng hp dung dch long th hot a ca cht phn ng c thay bng nng C (mol/l). V d i vi in cc Fe2+/Fe vi phn ng in cc l: Fe2+ + 2e Fe 25oC vi CFe 2 + = 106 mol/l th ta c gi tr th in cc ca cp Fe2+/Fe l:
EFe2+
o = EFe2 +

+
Fe

0,059 2 0,059 2

lg

CFe2 + CFe

Fe

hoc 3.4

EFe2+

= 0,441 +
Fe

lg 10 6 = 0,618 V

Phn loi in cc

Trong in ha c nhiu cch phn loi in cc v c th chia thnh mt s loi chnh nh sau:

3.4.1 in cc loi 1

7
in cc loi 1 l in cc lm vic thun nghch vi cation. a s cc in cc gm kim loi nhng vo dung dch mui ca n u thuc in cc loi 1 v c th vit dng tng qut sau: Men+/Me vi phn ng in cc: Men+ + ne Phng trnh Nernst c dng:
EMen +

Me

(3.9)

Me

= Eo n + Me

+
Me

0,059 Z

lg

a Men + a Me

25oC

(3.10)

V d 1: Zn2+/Zn hoc (ZnSO4/Zn) vi phn ng in cc: Zn2+ + 2e 25oC ta c:

EZn2 + EZn2 +

Zn +
Zn

Zn

= Eo 2 + Zn

0,059 2

lg

a Zn2 + a Zn

= 0,76 +
Zn

0,059 2

lg a Zn2 +

V d 2: Cu2+/Cu hoc (CuSO4/Cu) vi phn ng in cc: Cu2+ + 2e 25oC ta c:

ECu2 + ECu2 +

Cu +
Cu

Cu

o = ECu2 +

0,059 2

lg

aCu2 + aCu

= 0,34 +
Cu

0,059 2

lg aCu2 +

V d 3: Fe2+/Fe hoc (FeSO4/Fe) vi phn ng in cc: Fe2+ + 2e 25oC ta c:

EFe2+ EFe2+

Fe +
Fe

Fe

o = EFe2 +

0,059 2 0,059 2

lg

aFe2 + aFe

= 0,441 +
Fe

lg aFe2 +

Cc in cc kim loi trong hn hng tip xc vi dung dch mui ca n cng thuc vo in cc loi 1.

3.4.2 in cc loi 2
in cc loi 2 l in cc lm vic thun nghch vi anion. Thng thng in cc loi ny gm kim loi nhng vo dung dch mui t tan ca n. V d: in cc bc Cl / AgCl / Ag c phn ng in cc l: Ag+ + e Ag hoc AgCl + e Ag + Cl Ta thy rng nng Ag+ rt nh v mui AgCl rt t tan v bng:

C Ag =

TAgCl CCl

trong TAg l tch s tan ca mui AgCl, phng trnh Nernst i vi in cc bc 25oC l:
EAgCl
Ag

= Eo AgCl
Ag

+ +
Ag

0,059 1 0,059 1

lg CAg + lg TAgCl 0,059 lg CCl (3.11)

EAgCl
Ag

= Eo AgCl = Eo + Ag
Ag

trong : hoc Vy

Eo AgCl
Ag

0,059 1

lg TAgCl

EAgCl
Ag

= 0,2224 V NHE khi CCl = 1M = 0,2224 0,059 lg CCl

EAgCl
Ag

Gi tr th in cc bc ph thuc vo nng ion Cl (bng 3.1). Bng 3.1 Gi tr th in cc bc ph thuc vo nng ion Cl 25oC in cc 1,00N KCl, AgCl/Ag 0,10N KCl, AgCl/Ag 0,10N HCl, AgCl/Ag Gi tr th (V) v NHE 0,2384 0,2900 0,2890

Trng hp tng qut i vi in cc loi 2 l: X, MexXy/Me, trong X l halogen, phng trnh Nernst 25o C l:
EMex X y
Me

= Eo x X y Me
Me

0,059 y

lg a y X

(3.12)

V d 2: in cc calomen, in cc ny c s Cl, Hg2Cl2/Hg. Phn ng in cc: Hg2Cl2 + 2e 2Hg + 2Cl 0,059 lg CCl (3.13) p dng cng thc 3.12, gi tr th in cc calomen c xc nh theo phng trnh:
EHg 2Cl2
Hg o = EHg 2Cl2 Hg

hoc

EHg 2Cl2

Hg

= 0,2768 0,059 lg CCl

Gi tr th in cc calomen thay i theo hot ion Cl v ph thuc nhit . Bng 3.2. S ph vo nng ion Cl v nhit thuc ca gi tr th in cc calomen

Nng dung dch KCl 0,1N 1,0N Bo ha

Gi tr th in cc trong khong 0o 100oC

EHg 2Cl2 EHg 2Cl2 EHg 2Cl2

= 0,336 7.105(t 25oC)

Hg

= 0,2801 2.104(t 25oC)

Hg

= 0,2412 7.105(t 25oC)

Hg

in cc calomen (xem hnh 3.4) cho gi tr th rt n nh, do c dng ph bin, song v s dng thy ngn nn ngy nay c xu hng thay th in cc calomen bng in cc bc.

8 6

4 3 2 1 6
Hnh 3.3 Cu to in cc bc 1. Dung dch HCl; 2. Mui AgCl; 3. Dy bc kim loi; 4. Dy dn in; 5. L b sung dung dch; 6. L xp Hnh 3.4 S in cc calomen

5 4 3 2 7 1

1. L xp; 2. L xp; 3. Hg2Cl2; 4. Thy ngn; 5. Dy platin; 6. Dy dn in; 7. Dung dch KCl; 8. L np dung dch KCl

V d 3: in cc thy ngn sunfat, Hg2SO4/Hg. Phn ng in cc l: Hg2SO4 + 2e 2Hg + SO42

0,059 2

Phng trnh Nernst tnh gi tr th in cc:

EHg 2SO4

= 0,6156
Hg

lg CSO2
4

(3.14)

10
3.4.3 in cc kh
Thng thng cc in cc kh gm kim loi tr, v d platin c din tch rt rng hp th kh, kh tip xc vi dung dch cht in li c cha ion ca nguyn t dng kh. Vic nghin cu cc in cc kh hiro v oxi rt c ngha i vi vic gii thch n mn in ha ca kim loi trong cc mi trng cht in li, chng ta s ln lt xt cc in cc kh hiro v oxi.

H2

3 2

H2

Hnh 3.5 S in cc kh hiro 1. Platin; 2. Dung dch Hx+ 3. Cu ni

V d 1: in cc hiro (xem hnh 3.5). S in cc hiro: Hx+/H2(Pt) Phn ng xy ra trn in cc: 2H+ + 2e H2 C th xem in cc hiro l in cc lm vic thun nghch vi cation. Phng trnh Nernst tnh gi tr th in cc 25oC:

E2H+

H2

o = E2H+

+
H2

0,059 2

lg

a2 + H PH2

(3.15)

Nu p sut ca kh hiro bng n v PH2 = 1 atm v aH+ = 1 th ta c:

11
o = E2H+

E2H+

= 0,0000 V
H2

H2

v gi l th in cc tiu chun ca hiro. Ngi ta dng in cc tiu chun hiro xc nh th in cc tiu chun ca cc in cc khc. V vy ta c bng gi tr th in cc tiu chun ca cc in cc theo thang hiro (k hiu l NHE hoc SHE), khi PH2 = 1 atm phng trnh 3.15 c dng:
E2H+

= 0,059pH
H2

(3.16)

hoc t rH = lg PH2 ta c:
E2H+

= 0,059 + 0,0295rH
H2

(3.17)

in cc ny cng knh, d b ng c lm sai lch gi tr th in cc. Ngy nay ngi ta c th thay n bng in cc calomen, do c thang th calomen (SCE) hoc thay bng in cc bc v ta cng c thang chun theo in cc bc. V d 2: in cc kh oxi Cu to in cc oxi: OH / O2(Pt) Khc vi in cc hiro, in cc oxi l in cc khng thun nghch v oxi c th phn ng vi kim loi b hp ph. Phn ng in cc trong mi trng kim: O2 + 4e + 2H2O
o EO2 OH

4OH

(3.18)

= 0,401 V (NHE)

Trong mi trng axit: O2 + 4e + 4H+

o EO2 H2O

2H2O

(3.19)

= 1,229 V (NHE)

V mt ng hc cc phn ng trn u c xem l thun nghch, do th cn bng ca chng ng vi cc gi tr sau: i vi phn ng (3.18):
o EO2 OH

= 0,401 + 0,059 lg

1/ PO2 4

aOH

(3.20)

i vi phn ng (3.19):
o EO2 H2O

= 1,229 + 0,059 lg aH+ .PO2

1/4

(3.21)

12
Hai phng trnh (3.20) v (3.21) l tng ng nhau nu thay th hot OH aH2 =
KW a H+

1014 aH+

; nu t lg PO2 = rO th cc phng trnh (3.20) v (3.21) c dng:

EO2

= 1,229 0,059pH 0,0148rO

H2O

(3.22)

3.4.4 in cc oxi ho kh (Redox)

in cc oxi ho kh l mt h in ho gm mt dy dn kim loi tr (v d Pt) tip xc vi dung dch cha cht oxi ho kh. V d 1: in cc oxi ho kh thun tu, trong dung dch ch c mt h oxi ho kh Fe3+, Fe /Pt vi phn ng in cc:
2+

Fe3+ + e

Fe2+

Phng trnh Nernst tnh th in cc:

EFe3 +
Fe2 + o = EFe3 +

+
Fe2 +

0,059 1 lg

lg

aFe3 + aFe2 +

hoc

EFe3 +

= 0,771 +
Fe2 +

0,059 1

aFe3 + aFe2+

(3.23)

Trong trng hp tng qut: Ox + Ze v

EOx
Re d

Red
o = EOx

+
Re d

0,059 Z

lg

aOx a Re d

(3.24)

V d 2: in cc oxi ho kh hn hp. i vi trng hp ny, trong dung dch ngoi cc cht oxi ha v kh cn c cc cht ng vai tr l mi trng phn ng, v d H+ hoc OH. V d: in cc MnO4 , Mn2+, H+/Pt Phn ng in cc: MnO4 + 5e + 8H+ Mn2+ + 4H2O
o

(3.25)
a MnO .a8 + H
4

Phng trnh Nernst tnh th in cc 25 C :

EMnO ,H+
4

Mn2 +

= Eo ,H+ MnO
4

+
Mn2 +

0,059 5

lg

a Mn2 + .a4 2O H

hoc

EMnO ,H+
4

= 1,507 0,0945pH + 0,0118 lg

Mn2 +

a MnO

a Mn2 + .a4 2O H

3.4.5

in cc oxit kim loi

in cc oxit kim loi c cng thc MexOy/Me, OH.

13
Phn ng in cc: MexOy + yH2O +2ye xMe + 2yOH (3.26) Loi in cc ny thng xy ra trong qu trnh to mng th ng kim loi. V d 1: in cc oxit antimon c cng thc: Sb2O3/Sb, OH trn b mt c ph lp Sb2O3 hoc lp Sb(OH)3. Phn ng in cc: Sb2O3 + 6e + 3H2O
o = ESb2O3

2Sb + 6OH 0,059 lg aOH (3.27)

Phng trnh Nernst tnh th in cc ca in cc ny 25oC l:

ESb2O3
Sb,OH

Sb,OH

i vi mi trng axit in cc ny c cu to: Sb2O3, H+/Sb hoc Sb(OH)3, H+/Sb vi phn ng in cc: Sb2O3 + 6e + 6H+ 2Sb + 3H2O
aSb2O3 .a6 + H
2 aSb .a3 2O H

Phng trnh Nernst tnh th in cc ca in cc ny 25oC:

ESb O
2 3 .H +

o = ESb O .H+ Sb
2 3

Sb

0,059 6

lg

Nu chp nhn aSb2O3 = 1, aSb = 1 v aH2O = 1 th ta c:

ESb O
2 3 .H +

o = ESb O .H+ Sb
2 3

0,059pH
Sb

(3.28)

V d 2: in cc oxit thu ngn, cu to ca in cc: HgO/Hg, OH. Phn ng in cc: HgO + 2e + H2O hoc HgO + 2e + 2H+ Hg + 2OH Hg + H2O
aHgO aHg .a2 OH

Phng trnh gi tr th in cc 25oC:

EHgO
Hg,OH
o = EHgO

+
Hg,OH

0,059 2

lg

Nu aHgO = 1, aHg = 1 th ta c:
EHgO
Hg,OH
o = EHgO Hg,OH

0,059 lg aOH

(3.29)

C th dng in cc ny lm in cc so snh nu mi trng c pH > 7, cn trong mi trng axit th oxit thu ngn b ho tan.

14
3.5 S dng gi tr th in cc tiu chun xt chiu hng phn ng
Bng gi tr th in cc tiu chun c gii thiu trong phn ph lc bao gm cc gi tr th in cc tiu chun khc nhau v chng c xp theo chiu tng gi tr th in cc, s dch chuyn t gi tr m nht n gi tr dng nht (t 3,02 V 3,06 V). Cp oxi ho kh c th tiu chun cng m th cht kh ca cp cng d dng nhng in t v kh nng nhn in t ca cht oxi ho cng km. Hy xt chiu hng ca phn ng oxi ho kh xy ra khi trn 2 cp oxi ho kh vo nhau. V d xt hai cp oxi ho kh Ce4+/Ce3+ v Fe3+/Fe2+ ng vi cc gi tr th tiu chun 1,61 V v 0,77 V. Phn ng ring ca cc cp l: Ce4+ + e Ce3+ T th cn bng ca n 25oC bng:
ECe4 +

= 1,61 + 0,059 lg
Ce3 +

aCe4 + aCe3 +

(3.30)

Fe3+ + e

Fe2+

Vi th cn bng 25oC bng:

EFe3 +

= 0,77 + 0,059 lg
Fe2 +

aFe3 + aFe2 +

(3.31)

Sau khi trn hai h oxi ho kh trn vo nhau v phn ng t trng thi cn bng nu cc phng trnh (3.30) v (3.31) bng nhau: 1,61 + 0,059 lg v vi
aCe4 + aCe3 +

= 0,77 + 0,059 lg Ce3+ + Fe3+ = 1014

aFe3 + aFe2 +

Ce4+ + Fe2+ Kcb =

aCe3 + .aFe3 + aCe4 + .aFe2 +

Kcb rt ln, ngha l phn ng xy ra vi nng cht to thnh CCe3 + v CFe3 + rt ln. Vy phn ng xy ra theo hng oxi ho ion Fe2+ thnh Fe3+ v kh ion Ce4+ thnh ion Ce3+. Ta cng c th ly v d khc xt chiu hng phn ng xy ra khi cho kim loi hot ng phn ng vi dung dch mui y kim loi km hot ng ra khi mui. V d nhng kim loi st vo dung dch CuSO4. Cc phn ng xy ra 25oC: Fe2+ + 2e
EFe2+

Fe
0,059 2 lg aFe2 +

= 0,4402 +
Fe

(3.32)

Cu2+ + 2e
ECu2 +

Cu
0,059 2 lg aCu2 +

= 0,3370 +
Cu

(3.33)

15
Ti trng thi cn bng: Fe + Cu2+ Fe2+ + Cu v cc phng trnh (3.32) v (3.33) bng nhau ta c: 0,4402 + vi
0,059 2 aFe2 + aCu2 + lg aFe2 + = 0,3370 + 0,059 2 lg aCu2 +

Kcb =

= 1026

Hng s cn bng rt ln, vy phn ng xy ra theo chiu kim loi st chuyn thnh ion Fe2+ v ion Cu2+ chuyn thnh ng kim loi mt cc hon ton, ngha l nu hot ca ion Fe2+ = 1 th hot ca ion Cu2+ = 1026, khi trong dung dch nng ion Cu2+ rt nh. Tt c nhng nguyn t dng kh trong dy th oxi ha kh c in th m hn th in cc tiu chun hiro u khng bn nhit ng hc khi tip xc vi nc. V d 1 : Kim loi Na trong cp oxi ha kh Na+/Na c cho vo nc s phn hy nc gii phng hiro: Na + HOH = Na+ + OH +
1 2
o ENa+

= 2,71 V, khi
Na

H2
Eo 3 + Ti

V d 2: Cho Ti2+ trong cp oxi ha kh Ti3+/Ti2+ vi cho vo nc s phn hy nc gii phng hiro: Ti2+ + HOH = Ti3+ +OH +
1 2

= 0,37 V, khi
Ti 2 +

H2

Tt c nhng in cc c th in cc tiu chun m hn so vi th in cc oxi u khng bn nhit ng hc khi chng tip xc vi oxi v nc, dn n chng s d dng kh oxi, v d kim loi st tc dng vi oxi trong khng kh theo phn ng: Fe + hoc Cu +
1 2 1 2

O2 + H2O = Fe2+ + 2OH O2 + H2O = Cu2+ + 2OH

o ( EFe2+

= 0,44 V)
Fe

o ( ECu2 +

= 0,34 V)
Cu

Trong trng hp vi nhng cp oxi ha kh c th in cc tiu chun dng hn th o in cc tiu chun ca oxi ( EO2 = 1,229 V), trng thi cn bng chng khng bn v
H2O

mt nhit ng hc v lm phn hy nc gii phng oxi. V d trong dung dch cha ion o Ce4+ ( ECe4 + = 1,61 V) d dng chuyn thnh ion Ce3+ v gii phng hiro theo phn ng:
Ce3 +

Ce4+ +

1 2

H2O = Ce3+ + H+ +

1 4

O2

nh gi bn nhit ng hc ca cc in cc trong dung dch nc ngi ta dng gin th - pH (xem phn tip theo) ca Poubaix.

16
Da vo cc gi tr th in cc tiu chun bit tnh gin tip th in cc tiu chun ca mt cp oxi ha kh kh xc nh.
o V d: Tnh EFe3 + Fe o khi bit EFe2 + Fe o = 0,44 V v EFe3 +

= 0,77 V. tnh c gi tr
Fe2 +

th tiu chun ca cp Fe3+/Fe ta lp chu trnh sau:

Go3 3e 1e

Fe

Fe3+
Go1

2e Go2

Fe2+
Da vo chu trnh trn ta c:
o o o G3 = G2 + G1

v suy ra:
o o o 3FE3 = 2FE2 + FE1 o 3E3 o o = 2E2 + E1

Vy
o o E3 = EFe3 +

=
Fe

o o 2E2 + E1

3
Fe o + EFe3 + Fe2 +

hoc

o EFe3 +

=
Fe

o 2EFe2 +

= 0,036 V

3.6 Pin in (Pin Ganvani hoc mch in ha)

3.6.1 Pin in v cc phn ng xy ra trong pin Mch in ha l mt h in ha gm t nht 2 in cc ghp li. Vic nghin cu v pin in rt c ngha khoa hc trong vic gii thch n mn in ha. Khi m t mt pin in c quy c nh sau: Cc in cc c xp thnh mt hng, gia cc mt tip xc c quy c: mt gch thng ng l gii hn gia pha rn v pha lng, hai gch thng l mt gii hn pha gia hai cht lng tip xc (hoc l cu ni ca hai dung dch cht in li). in cc t bn tri l cc m c gi l anot, in cc t bn phi l in cc dng c gi l catot. V d: Ghp hai in cc CuSO4/Cu v ZnSO4/Zn thnh pin in: () Zn|ZnSO4 Cu|CuSO4 (+)

17

Hnh 3.6 S pin in Danien - Jacobi (pin ng km) 1. Dung dch ZnSO4; 1. Dung dch CuSO4; 2,2. Km v ng kim loi; 3. Cu ni 2 dung dch (cu aga); 4. Ampe k

Khi khp kn mch bng dy dn loi 1 (dy ng) pin s hot ng v c ch th qua ng h ampe, trn hai in cc xy ra cc phn ng sau: Trn anot (): Trn catot (+): Zn 2e Zn2+ Cu2+ + 2e Cu ; ;
Eo 2 + Zn
o ECu2 +

= 0,76 V
Zn

= + 0,34 V
Cu

Phn ng chung ta c: Zn + Cu2+ Zn2+ + Cu

(3.34)

3.6.2 Sc in ng ca pin in
Bin thin th ng nhit ng p ca phn ng (3.34) v cng in ca pin Danien Jacobi c quan h vi nhau theo phng trnh: G = AMax = ZF (3.35) trong : AMax l cng cc i hu ch; sc n ng ca pin in; F hng s Faraday (96493 C); Z s electron trao i. Theo quy c, sc in ng ca pin in c tnh theo cng thc sau: = E+ E trong : E+ th in cc dng; E th in cc m. T phng trnh 3.34, da vo bin thin ho th c quan h vi sc in ng ca pin in rt ra c cng thc tnh sc in ng ph thuc vo nng cc cht phn ng xy ra trong pin. Vy: = o +
RT ZF lg a Zn .aCu2 + a Zn2 + .aCu

(3.36)

(3.37)

18
Phn ng 25oC th ta c: = o +
0,059 Z lg a Zn .aCu2 + a Zn2 + .aCu

Vi phn ng tng qut xy ra trong pin l: 2 Red2 + 1 Ox1 Vy = +

o

2 Ox2 + 1 Red1
lg
1 a 2 d .aOx Re
2 1

RT ZF

1 aOx .a 2 d Re
' ' 2

(3.38) , khi hot cc cht phn

Re d 2

o Vi iu kin th in cc tiu chun EOx1

Re d1

o > EOx2

ng bng n v ( aOx1 , aOx2 , a Re d1 , a Re d2 = 1) th sc in ng ca pin bng sc in ng tiu chun o. i vi pin Danien - Jacobi sc in ng tiu chun bng:
o o = ECu2 + Cu

Eo 2 + Zn

= 0,337 ( 0,76) = 1,097 V

Zn

Nu aCu = aZn = 1 ; phng trnh (3.37) c dng: = 1,097 +

0,059 2 lg aCu2+ a Zn2 +

(3.39)

Vy sc in ng ca pin in ph thuc vo hai gi tr l sc in ng tiu chun v nng cc cht tham gia phn ng.

3.6.3 Phn loi pin in

Pin in c nhiu loi, song c th chia lm hai nhm chnh sau y: 1. Pin ho hc Pin ho hc l mt h in ho gm hai in cc c tnh cht ho hc khc nhau ghp li, n c phn chia thnh nhiu loi a) Pin ho hc n gin Pin ho hc n gin l h in ho gm hai in cc khc nhau nhng c chung cht in li ghp li. V d 1: Pin hiro v oxi, pin ny c s Pt, H2/H2O/Pt, O2. Phn ng chung xy ra trong pin l: H2 +
1 2

O2 + H2O

2H+ + 2OH

(3.40)

Gi tr sc in ng 25oC l: = o 0,059lgK +
0,059 2
1/ lg PH2 .PO2 2

= o 0,059lg1014 +

0,059 2

1/ lg PH2 .PO2 2

19
1/ = o + 0,0295 lg PH2 .PO2 2

(3.41)

V d 2: Pin tiu chun Weston S pin: () Hg(25% Cd) / CdSO4(dd) / HgSO4 / Hg (+) Trong pin dung dch CdSO4 c dng chung cho c hai in cc, cc m l in cc loi 1, cc dng l in cc loi 2, phn ng xy ra trong pin l: Cd + HgSO4 Cd2+ +2Hg + SO42 Gi tr sc in ng: = o = o
RT 2F RT F lg aCd2 + .aSO2
4

lg a CdSO4

(3.42)

Vi dung dch CdSO4 bo ho, gi tr s ca pin bng 1,018 V, gi tr ny rt n nh v ph thuc vo nhit : = 1,018 4.105(t 20oC) V Cc cquy axit, cquy kim c xp vo loi pin ha hc n gin. b) Pin ho hc phc tp Pin ho hc phc tp l mt h in ho gm hai in cc loi 1 khc nhau ghp li. V d Pin Danien - Jacobi. S pin: () Zn / ZnSO4 // CuSO4 / Cu (+) Khp kn mch xy ra phn ng tng cng: Cu2+ + Zn Cu + Zn2+ (3.43) Trong n mn in ho thng tn ti loi pin ny khi c hai kim loi tip xc vi nhau c t trong mi trng cht in li (s nghin cu phn sau). i vi pin Pin Danien - Jacobi sc in ng c tnh: = o + = 1,1 +
0,0591 2
a Cu2+ a Zn2+ a Cu2+ a Zn2+

lg lg

0,0591 2

Khi pin nm trng thi cn bng th hng s cn bng Kcb ca phn ng c tnh: 1,1 =
0,0591 2

lgKcb

Suy ra: Kcb = 1037 ngha l khi a Zn2 + = 1 th aCu2 + = 1037, khi nng ion Cu2+ rt nh v km hon ton b n mn, qu trnh ho tan km y xy ra mt cch t din bin. 2. Pin nng

20
Pin nng l mt h in ho gm cc in cc ghp li to ra pin in, song nng cht dn in loi 2 hoc cht dn in loi 1 khc nhau. Loi pin ny tn ti trong cc loi n mn in ho, v d s n mn in ho do s chnh lch nng oxi (n mn khe, n mn l). Sau y l mt s v d: V d 1: Pin nng () Ag / AgNO3 // AgNO3 / Ag (+) a1 a2 Gi thit a1(AgNO 3 ) < a2(AgNO 3 ). Ti anot xy ra phn ng: () Ag Ag+ (a2)
+

1e Ag+ (a1) Ag+ (a1)

(+) Ag+(a2) + 1e Ag Qu trnh pin hot ng gn lin vi s gim hot Ag+ ti khu catot v tng hot Ag ti vng anot. Pin khng hot ng khi hot Ag+ ti hai vng catot v anot bng nhau. Sc in ng: =
RT F

lg

a2 a1

v 25oC.
a2 a1

= 0,0591lg Khi nng

a2 a1

= 10 th sc in ng E = 0,0591 (V).

V d 2: Pin nng oxi Trong n mn in ho ho tan kim loi th oxi ng vai tr l cht nhn in t. Song s c mt ca oxi ti cc vng khc nhau to ra cc in cc oxi c nng oxi khc nhau. Khi khp kn to thnh pin nng oxi v lm tng tc n mn (xem chi tit trong phn n mn kim loi trong iu kin c mt nng oxi khc nhau).

3.7 Phng php o sc in ng v ng dng

o sc in ng ca mt pin in cho php suy ra th in cc ca kim loi b n mn trong mi trng cht in li. Trong mc nht nh, vic so snh th in cc n nh ca kim loi trong mi trng n mn cho php suy on bn vng chng n mn ca vt liu. V vy, vic o chnh xc gi tr th in cc c ngha nht nh. o chnh xc sc in ng ca pin in ngi ta dng phng php b chnh. S cu b chnh o sc in ng ca pin in c trnh by trn hnh 3.7 v trong : iu kin o: cquy > x. Nguyn tc o v tnh x: Di chuyn con chy K trn in tr AB sao cho khng c dng i qua pin x v in k G ch s khng. Khi cu cn bng v ta c:

21
cquy AB x AK Vy:
acquy E

AB AK

Hnh 3.7 S cu b chnh o sc in ng pin in cquy: Sc in ng cquy; AB: Dy in tr u; x: Sc in ng pin o; w: Sc in ng pin chun; G: in k; K: Con chy tip xc; K: Con chy tip xc; O: Tip xc ng ngt in

Rt ra: x = cquy.
AB AK

(a)

V gi tr in ng cquy khng hon ton chnh xc nn phi chnh li gi tr cquy bng pin chun Weston c gi tr w = 1,018 V. Gi tr ny khng thay i theo v tr song c thay i theo nhit v kh nng phc hi ca pin ny rt nhanh. Tng t trng hp xc nh, thay x bng w (xem hnh 3.7) v m tip xc O, ta li di chuyn con chy K, tm v tr ng vi in k G ch s khng v d im K, ta c: cquy AB ; w = AK. Ta c: cquy = w.
AB AK AK ' AB

(b)

Kt hp hai cng thc (a) v (b) ta c: x = w.

AK AK = 1,018. (V) AK ' AK ' AB
AB

Vy ta ch cn xc nh AK v AK l o c sc in ng E ca pin in. Ch : c th thay dy in tr u AB bng cc hp in tr.

22
Ngy nay php o sc in ng ca pin in c ng dng rt rng ri trong vic ch to cc thit b o: o pH, o th in cc, chun in th ca phng php in ho... Sau y l mt s v d ng dng php o sc in ng ca pin in. Nh bit, thng qua vic o nhit lng k xc nh c hiu ng nhit phn ng, hoc nng lng G. Mt khc c th o sc in ng pin in tnh cc hm nhit ng. Ta xt phn ng xy ra trong pin in Danien - Jacobi: Cu2+ + Zn Ch to pin in theo hnh (3.6). o sc in ng pin in 25oC thu c gi tr o . Vy: G = 2Fo = 2 96493. o G = H TS V: Vy: hoc: v
G = S hoc 2F T p = S T p

Cu + Zn2+

(c)

tnh G phn ng ny bng cch o sc in ng ca pin Danien - Jacobi:

(3.44) (3.45) (3.46) (3.47)

tnh H ca phn ng (c) ta p dng:

G = H T2F

T p T p

2Fo = H T2F o =
H
2F

+T

T p

(3.48)

tnh H ca phn ng theo (3.48) trc ht phi xc nh h s nhit ca sc in ng ra

bng cch o sc in ng ph thuc nhit v t cc s liu th nghim suy T p

. T p

Phng trnh (3.48) cn c dng: o =

Qp + T 2F T p

(3.49)

trong Qp gi l nhit phn ng. Phng trnh (3.49) cho bit quan h gia sc in ng v nhit phn ng.

23
= 0 th ton b nhit phn ng chuyn thnh cng in v < 0 th ch T p T p

Nu

c mt phn nhit phn ng chuyn thnh cng in, trong mt phn chuyn cho mi trng. Vy khi pin lm vic th mi trng xung quanh nng ln. Nu
> 0 th cng in thu c ln hn nhit phn ng chuyn thnh cng. T p

sinh cng in, pin lm vic thu nhit ca mi trng, v th khi pin lm vic mi trng s b gim nhit . Mt v d khc, o sc in ng pin in tnh pHx ca mi trng. Mun o sc in ng tnh pHx ca mi trng ta phi chn hai in cc to ra pin: + 1 in cc so snh (in cc bc hoc Calomen) + 1 in cc ch th Hx+ (in cc hiro hoc in cc thu tinh, in cc oxi ho kh quinon v hiroquinon). y ta chn in cc hiro 2Hx+ / H2 (Pt), vi PH2 = 1 atm. Ghp cc in cc to thnh pin in 25oC: () (Pt) H2 / 2Hx+ / Cl, AgCl / Ag+ (+) o sc in ng ca pin ny ta c o v theo quy c ta c: o = E(+) E() hoc Vy: o = 0,2222 V ( 0,0591pHx) pHx =
o 0,2222

0,0591

(3.50)

(Trong th in cc bc chn bng 0,2222 V).