Chng VIII & IX

PIN IN HA & TH IN CC
CHUN TH OXY HA KH

Ts. Phm Trn Nguyn Nguyn

ptnnguyen@hcmus.edu.vn

1. Phn ng oxy ha kh
Phn ng lin quan n s chuyn in t gia cc
tiu phn ca phn ng

Ox1 + Kh 2 R Kh1 + Ox 2
Ox1 + ne R Kh1 (bn phn ng kh)
Kh 2 R Ox1 + ne (bn phn ng oxy ha)
Ox = cht oxy ha nhn in t (b kh), lm gim s
oxy ha
3+
2+

Fe + e R Fe

Kh = cht kh cho in t (b oxy ha), lm tng s oxy

ha

2I R I 2 + 2e

Cc cht ng vai tr oxy ha hay kh ty thuc vo th

kh ca chng

Cu(s) + 2Ag+(aq)

Cu(s) + Zn2+(aq)

Cu2+(aq) + 2 Ag(s)

Khng p.ng

Cu/dd Ag+

Cu/dd Zn2+

2. Cn bng phn ng oxy ha - kh

Sn +2 + Fe +3 R Sn +4 + Fe +2
Sn +2 R Sn +4 + 2e( Fe +3 + e R Fe +2) x 2
Sn 2+ + 2Fe3+ R Sn 4+ + 2Fe 2+

2. Cn bng phn ng oxy ha - kh

Fe 2+ + MnO-4 R Fe3+ + Mn 2+
MnO -4 + e- ? R Mn 2+
-1 = 1(x)Mn + 4(-2)O
x = +8 - 1 = +7

+2

MnO -4 + 5e- R Mn 2+
MnO -4 + 5e- R Mn 2+ + 4H 2 O
MnO -4 + 5e- + 8H + R Mn +2 + 4H 2 O (1)
(

Fe 2+ R Fe3+ + e

) x5

(2)

5Fe2+ + MnO-4 + 8H + R 5Fe3+ + Mn 2+ + 4H 2 O

5

Cn bng phn ng oxy ha - kh

Fe 2+ + Cr2 O 72- R Fe3+ + Cr 3+

Cr2 O72- + e- ? R Cr 3+

6Fe 2+ + Cr2 O72- + 14H + R 6Fe3+ + 2Cr 3+ + 7H 2 O

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3. Chiu ca phn ng oxy ha- kh

9 Mch in oxy ha-kh

Fe 2+ + Ce4+ R Fe +3 + Ce3+
s di chuyn ca cc
e- kt qa ca p.
ha hc
Hiu th o c
gia 2 cc ca mch
= hiu th oxy ha kh
ca cc nguyn t to
nn h = sc in
ng ca pin Galvanic.
-(PtI) Fe2+Fe3+Ce3+Ce4+(PtII)+

Fe2+ b oxy ha
(in cc anode)

Zn Zn2+ + 2e-

Ce4+ b kh
(in cc cathode)

Cu2+ + 2e- Cu

- Zn(s) , Zn2+(aq) || Cu2+(aq) , Cu(s) +

Ecell = 1.103

4. Th oxy ha- kh
9 in cc hydro chun (SHE)
so snh kh nng oxy
ha kh ca cc nguyn t
v lp mch Galvanic gm
cp cn kho st v in cc
hydro chun
in cc hydro chun (SHE)
Pt|H2(g,1atm)| 2H+(a = 1)
2 H+ (a = 1) + 2e- H2 (g,1atm)
Qui c: E = 0 V
9

Th chun
Pt|H2(g, 1 atm), H+ (a = 1) || Cu2+(1 M), Cu(s) Ecell = ?
cathode
anode
Ecell = Ecathode - Eanode
Ecell = ECu2+/Cu - EH+/H2
0.340 V = ECu2+/Cu - 0 V
ECu2+/Cu = +0.340 V
H2 + Cu2+ H+ + Cu(s)

Ecell = 0.340 V
10

o th chun

anode

cathode

H2 2H+ + 2e-

Cu2+ + 2e- Cu

E0Cu2+/Cu = 0,34 V

cathode

anode

2H+ + 2e- H2 Zn Zn2+ + 2e-

E0Zn2+/Zn = -0,763 V

11

S mch Galvanic ca st clorua vi in cc hydro

(Pt) H2, 2H+ || Fe2+, Fe3+ (Pt)
hay

SHE || Fe2+, Fe3+ (Pt)

hiu s th trn cc cc ca mch galvanic = +0,771 V

Gi tr dng ch tnh oxy ha ca Fe3+ > H+
th o c vi in cc hydro chun khi nng ca
cc ion = 1M, nhit 250C gi l th chun (E0)
Th in cc cng dng tnh oxy ha ca tc nhn oxy
ha cng mnh, v dng kh ca n c tnh kh cng yu

Ce 4+ + e R Ce3+ E 0 = 1,61V
Ce4+ l tc nhn oxy ha mnh, Ce3+ tc nhn kh yu

Zn 2+ + 2e R Zn E 0 = 0,76V
Zn2+ l tc nhn oxy ha yu, Zn tc nhn kh mnh

12

TH CHUN

Tnh kh tng

Tnh oxy ha tng

Bn phn ng
F2 + 2e- 2FTc nhn
Tc nhn
MnO4- + 5e- Mn2+
Oxy ha
kh
Ce4+ + e- Ce3+ (in HCl)
O2 + 4H+ + 4e- 2H2O
Ag+ + e- Ag(s)
Cu2+ + 2e- Cu(s)
2H+ + 2e- H2(g)
Cd2+ + 2e- Cd(s)
Fe2+ + 2e- Fe(s)
Zn2+ + 2e- Zn(s)
Al3+ + 3e- Al(s)
K+ + e- K(s)
Li+ + e- Li(s)

Eo (V)
2.890
1.507
1.280
1.229
0.799
0.339
0.000
-0.402
-0.440
-0.763
-1.659
-2.936
-3.040

13

Sc in ng ca pin
- (PtI) Sn2+, Sn4+ Fe3+, Fe2+(PtII) +
anode
cathode
0
Sn 4+ + 2e- Sn 2+ , E Sn
= 0,154
4+
/Sn 2+
Fe3+ + e - Fe 2+ , E 0Fe3+ /Fe2+ = 0, 771

Anode: Xy ra qu trnh oxy ha cht kh mnh (bn tri)

Cathode: Xy ra qu trnh kh cht oxyha mnh (bn phi)

E pin = E right E left = E cathode E anode = E + E 0

E pin = E 0Fe3+ /Fe2+ ESn
4+
/Sn 2+
= 0, 771 0,154

= 0, 617

* Khi pin c thit lp, s ca pin lun dng

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Tnh sc in ng ca pin c thit lp t 2 bn pin sau

Fe3+ + e R Fe 2+ E 0 = 0,771V
I3- + 2e R 3I- E 0 = 0,5355V
vi E 0Fe3+ /Fe2+ > E 0I - /I3

E pin = E 0Fe3+ /Fe2+ E 0I- /I- = 0, 771 0,536 = 0, 235

3

2Fe3+ + 3I- = 2Fe 2+ + I3-

15

5. Phng trnh NERNST

Bn phn ng:
aOx + ne- bKh
Th ca bn pin ( 25 oC), E, c tnh nh sau:
a
RT [ Ox ]
E=E +
ln
nF [ Kh ] a

[ Ox ] a
0.05916
O
E=E +
log
[ Kh ] b
n

Eo = th in cc chun
R = hng s kh = 8.314 J/K-mol
T = nhit tuyt i (298K)
F = hng s Faraday = 9.649 x 104 C/mol
n = s in t

Mt dd gm Cr2O72- 10-3M v Cr3+ 10-2M. Tnh th ca bn

pin trong mi trng acid pH = 2

Cr2 O72- + 14H + + 6e R 2Cr 3+ + 7H 2 O

E = E Cr2O2-/Cr3+
0

[Cr O2- ][H + ]14

0.05916
2 7
= 1.06V
+
log
3+ 2

6
Cr

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5. Phng trnh NERNST

Xt ton b phn ng: Th ca ton phn ng

n2 Ox1 + n1 Kh2 R n1Ox 2 + n2 Kh1

0
0
0
E pin = E + E - & E pin = E + E
E pin = (E 0+ E 0- )

0.05916 [Ox 2 ]n1 [Kh1 ]n2

0.059
lg
lg Q
= E0
n2
n1
[Ox1 ] [Kh 2 ]
n1n2
n1n2

Cho pin Cu Fe iu kin chun (nng = 1M)

Cu2+ + 2e- Cu(s)
0.339 V
2+
-0.440 V
Fe + 2e Fe(s)
Phn ng Galvanic
Cu2+(aq) + Fe(s) Cu(s) + Fe2+(aq)
Fe|Fe2+(1M) || Cu2+(1 M)|Cu

E 0pin = E 0+ E 0 = 0,339 + 0, 440 = 0, 779V

17

p dng phng trnh Nernst tnh s ca pin sau, Epin.

(Pt) Fe2+(0.10 M),Fe3+(0.20 M)||Ag+(1.0 M)|Ag(s)
Fe2+(aq) + Ag+(aq) Fe3+(aq) + Ag (s)
Epin = Epin Epin = Epin -

0.05916
log Q
n

0.05916
[Fe3+]
log 2+
[Fe ] [Ag+]
n

E0pin = 0.799 V 0.771 V = 0.0280

Epin = 0.028 V 0.018 V = 0.010 V
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5. Phng trnh NERNST

Phn ng Galvanic
Fe|Fe2+ (1M) || Cu2+ (1M)|Cu
Cu2+(aq) + Fe(s) Cu(s) + Fe2+(aq) Epin = 0.779 V
E > 0 p.ng ca pin xy ra t nhin theo chiu thun
E < 0 p.ng ca pin xy ra t nhin theo chiu nghch
Nu pin chy trong thi gian di:
Cht p.ng b tiu th
Sn phm c hnh thnh
P.ng t n cn bng
Epin 0 : l do ht pin
E = 0 p.ng ca pin t cn bng
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5. Phng trnh NERNST- Th cn bng

Khi pin t n cn bng ( 250C) : Epin = 0
E pin = (E 0+ E 0- )

0.05916 [Ox 2 ]n1 [Kh1 ]n2

0.05916
lg
lg Q = 0
= E0
n2
n1
[Ox1 ] [Kh 2 ]
n1n2
n1n2

E pin = E 0

K = 10

0.05916
lg K = 0
n1n2

n1n 2 E o /0.05916

E0 > 0: K > 1
E0 < 0: K < 1
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Mi quan h gia nhit ng hc (G0), cn bng (Kcb)

v in ha hc
Kcb

G 0 = RT lnK eq
H
G0 =H-TS0

G0

o thnh
phn cb

E 0pin =

G 0 = nFE 0pin

Epin

RT
lnK eq
nF

E 0pin , E 0

S0
21

6. in cc so snh (Reference Electrode)

in cc bc (Ag/AgCl) in cc calomel (SCE)
bo ha bng dd KCl
bo ha bng dd KCl
Hg2Cl2 + e- Hg + Cl AgCl(s) + e Ag (s) + Cl
E = +0.197 V
E = +0.241 V

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6. in cc so snh
Eo = Eo - 0.241 (SCE)
Eo = Eo - 0.197 (Ag/AgCl)
Eo(SHE)

E(SCE)

E(Ag/AgCl)

Cu2+ + 2e- Cu(s)

0.339 V

0.098 V

0.142 V

Fe2+ + 2e- Fe(s

-0.440 V

-0.681 V

-0.637 V

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7. Chun oxy ha kh
Xy dng th biu din s thay i th oxy ha kh E
ca dung dch nh phn theo mc thm dd chun ca
cht oxy ha hay kh
Xy dng ng cong chun
th ca 100,0 mL dd Fe+2
0,100M vi 10,0mL; 50,0mL;
100mL, 200,0mL dd Ce+4
0,100M trong mi trng
acid HNO3.

Fe 2+ + Ce 4+ R Ce3+ + Fe3+
E 0Fe3+ /Fe2+ = 0,771V

E 0Ce4+ /Ce3+ = 1,61V

24

Xy dng ng cong chun th ca 100,0 mL dd Fe+2

0,100M vi 10,0mL; 50,0mL; 100mL, 200,0mL dd Ce+4
0,100M trong mi trng acid HNO3.
Phn ng chun :

Fe 2+ + Ce 4+ R Ce3+ + Fe3+

Thm V =10,0 mL Ce4+

VFe2+ M Fe2+ > VCe4+ M Ce4+

# mmol Ce4+ thm vo = 0,100M x 10,0 mL = 1.00 mmol

# mmol Fe3+ to thnh = 1.00 mmol
# mmol Fe2+ cn li = (0,100 M x 100,0 mL)-1,00 mmol = 9,00

E=E

0
Fe3+ / Fe 2+

0, 0592
[Fe3+ ]
+
log
n
[Fe2+ ]

E = 0, 771 + 0, 0592 log(1, 00 / 9, 00) = 0, 714V

25

Xy dng ng cong chun th ca 100,0 mL dd Fe+2

0,100M vi 10,0mL; 50,0mL; 100mL, 200,0mL dd Ce+4
0,100M trong mi trng acid HNO3.
Phn ng chun :

Fe 2+ + Ce 4+ R Ce3+ + Fe3+

Thm V =50,0 mL Ce4+

VFe2+ M Fe2+ > VCe4+ M Ce4+

# mmol Ce4+ thm vo = 0,100M x 50,0 mL = 5.00 mmol

# mmol Fe3+ to thnh = 5.00 mmol
# mmol Fe2+ cn li = (0,100 M x 100,0 mL)-5,00 mmol = 5,00

0, 0592
[Fe3+ ]
log
n
[Fe2+ ]
5, 00
E = 0, 771 + 0, 0592 log
= 0, 771V
5, 00

E = E 0Fe3+ / Fe2+ +

26

Xy dng ng cong chun th ca 100,0 mL dd Fe+2

0,100M vi 10,0mL; 50,0mL; 100mL, 200,0mL dd Ce+4
0,100M trong mi trng acid HNO3.
Phn ng chun :

Fe 2+ + Ce 4+ R Ce3+ + Fe3+

Thm V =100,0 mL Ce4+

VFe2+ M Fe2+ = VCe4+ M Ce4+

im tng ng
# mmol Ce4+ thm vo = 0,100M x 100,0 mL = 10,0 mmol
# mmol Fe3+ cb = 10,0 x ~ 10,0
# mmol Fe2+ cb = x
# mmol Ce3+ cb = 10,0 x ~ 10,0
# mmol Ce4+ cb = x
27

Xy dng ng cong chun th ca 100,0 mL dd Fe+2

0,100M vi 10,0mL; 50,0mL; 100mL, 200,0mL dd Ce+4
0,100M trong mi trng acid HNO3.
Phn ng chun :

Fe 2+ + Ce 4+ R Ce3+ + Fe3+

Thm V =100,0 mL Ce4+

im tng ng

E 0Fe3+ / Fe2+ +
E

0
Fe3+ /Fe2+

VFe2+ M Fe2+ = VCe4+ M Ce4+

E Fe3+ /Fe2+ = E Ce4+ /Ce3+

0, 0592
[Fe3+ ]
0, 0592
[Ce 4+ ]
0
=
+
log
E
log
Ce4+ /Ce3+
n
n
[Fe 2+ ]
[Ce3+ ]

0
Ce4+ /Ce3+

0, 0592
[Fe3+ ] [Ce3+ ]
=
= 0, 0592 log K cb
log
1
[Fe 2+ ] [Ce 4+ ]

K cb = 1, 7 x1014

28

Xy dng ng cong chun th ca 100,0 mL dd Fe+2

0,100M vi 10,0mL; 50,0mL; 100mL, 200,0mL dd Ce+4
0,100M trong mi trng acid HNO3.

Fe 2+ + Ce 4+ R Ce3+ + Fe3+

Phn ng chun :

Thm V =100,0 mL Ce4+

VFe2+ M Fe2+ = VCe4+ M Ce4+

E Fe3+ /Fe2+ = E Ce4+ /Ce3+

im tng ng

[Fe3+ ] [Ce3+ ] (10, 0)(10, 0)

K cb = 1, 7 x10 =
=
[Fe 2+ ] [Ce 4+ ]
( x)( x)
14

x = 7, 7 x107 mmol Fe 2+ = mmol Ce 4+

E = E 0Fe3+ / Fe2+ + 0, 0592 log[Fe3+ ] /[Fe2+ ] =

= 0, 771 + 0, 0592 log(10, 0 / 7, 7x107 ) = 1,19V

29

Xy dng ng cong chun th ca 100,0 mL dd Fe+2

0,100M vi 10,0mL; 50,0mL; 100mL, 200,0mL dd Ce+4
0,100M trong mi trng acid HNO3.

Fe 2+ + Ce 4+ R Ce3+ + Fe3+

Phn ng chun :

Thm V =100,0 mL Ce4+

VFe2+ M Fe2+ = VCe4+ M Ce4+

im tng ng

E cb = E Fe3+ /Fe2+ = E Ce4+ /Ce3+

E cb = E

0
Fe3+ /Fe2+

[Fe3+ ]
+ 0, 0592 log
[Fe 2+ ]

E cb = E

0
Ce4+ /Ce3+

[Ce 4+ ]
+ 0, 0592 log
[Ce3+ ]

2E cb = (E

0
Fe3+ /Fe2+

+E

0
Ce4+ /Ce3+

[Fe3+ ][Ce3+ ]
) 0, 0592 log
[Fe 2+ ][Ce 4+ ]

30

Xy dng ng cong chun th ca 100,0 mL dd Fe+2

0,100M vi 10,0mL; 50,0mL; 100mL, 200,0mL dd Ce+4
0,100M trong mi trng acid HNO3.
Phn ng chun :

Fe 2+ + Ce 4+ R Ce3+ + Fe3+

Thm V =100,0 mL Ce4+

VFe2+ M Fe2+ = VCe4+ M Ce4+

im tng ng

E cb = E Fe3+ /Fe2+ = E Ce4+ /Ce3+

2E cb = (E
Ti cb

0
Fe3+ /Fe2+

+E

0
Ce4+ /Ce3+

[Fe3+ ][Ce3+ ]
) 0, 0592 log
[Fe 2+ ][Ce 4+ ]

[Fe3+ ] = [Ce 4+ ] & [Ce3+ ] = [Fe 2+ ]

1
E cb = (E 0Fe3+ /Fe2+ + E 0Ce4+ /Ce3+ ) = 1,19V
2

31

Xy dng ng cong chun th ca 100,0 mL dd Fe+2

0,100M vi 10,0mL; 50,0mL; 100mL, 200,0mL dd Ce+4
0,100M trong mi trng acid HNO3.
Phn ng chun :

Fe 2+ + Ce 4+ R Ce3+ + Fe3+

Thm V = 200,0 mL Ce4+ VFe2+ M Fe2+ < VCe4+ M Ce4+

# mmol Ce4+ thm vo = 0,100M x 200,0 mL = 20.0 mmol
# mmol Ce4+ d = 20,0 -(0,100 M x 100,0 mL) = 10,0 mmol
# mmol Ce3+ to thnh = 10,0 mmol

0, 0592
[Ce 4+ ]
log
n
[Ce3+ ]
10, 0
E = 1, 61 + 0, 0592 log
= 1, 61V
10, 0

E = E Ce4+ / Ce3+ +

32

33

Tnh th ti im tng ng ca qu trnh chun

100,0 mL dd Fe+2 trong dd H2SO4 0,500M bng 100,0 mL
dd MnO4- 0,0200 M.
Phn ng chun :

5Fe2+ + MnO-4 + 8H + R 5Fe3+ + Mn 2+ + 4H 2 O

= 0, 771V

E 0Fe4+ / Fe3+

E 0Mn 2+ / MnO = 1, 51V

4

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8. Cch nhn ra im tng ng trong pp Oxy ha kh

T ch th
Chuyn mu do dung dch gy ra do lng d ca dd chun
Vi d: Chun KMnO4 (mu tm)
Ch th h tinh bt
Vi d: Chun Iod, ho tinh bt to phc vi I2 xanh m
Ch th oxy ha kh
Cht c mu thay i tu thuc vo th oxy ha kh

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