PIN I PIN I N H N H A & TH A & TH I I N C N C C C

CHU CHU N N TH TH OXY H OXY H A KH A KH

Ts. Phm Trn Nguyn Nguyn
ptnnguyen@hcmus.edu.vn
Chng Chng VIII & IX VIII & IX
2
1. Phn ng oxy ha kh
Phn ng lin quan n s chuyn in t gia cc
tiu phn ca phn ng
Ox = cht oxy ha nhn in t (b kh), lm gim s
oxy ha
1 2 1 2
Ox Kh Kh Ox + +
1 1
Ox Kh ne

+ (bn phn ng kh)

2 1
Kh Ox ne

+ (bn phn ng oxy ha)

Kh = cht kh cho in t (b oxy ha), lm tng s oxy
ha
Cc cht ng vai tr oxy ha hay kh ty thuc vo th
kh ca chng
3+ 2
Fe e Fe
+
+
-
2
2I I 2e

+
3
Cu(s) + 2Ag
+
(aq)
Cu
2+
(aq) + 2 Ag(s)
Cu(s) + Zn
2+
(aq)
Khng p.ng
Cu/dd Ag
+
Cu/dd Zn
2+
4
2. Cn bng phn ng oxy ha - kh
+2 +3 +4 +2
Sn Fe Sn Fe + +
+2 +4 -
Sn Sn 2e +
+3 +2
Fe Fe e

+ x 2
(
)
2+ 3+ 4+ 2+
Sn 2Fe Sn 2Fe + +
5
2. Cn bng phn ng oxy ha - kh
2+ - 3+ 2+
4
Fe MnO Fe Mn + +
- - 2+
4
MnO e ? Mn +
-1 = 1(x)
Mn
+ 4(-2)
O
+2
x = +8 - 1 = +7
- - 2+
4
MnO 5e Mn +
- - 2+
4 2
MnO 5e Mn 4H O + +
- - +2
4 2
MnO 5e 8H Mn 4H O (1)
+
+ + +
2+ 3+
Fe Fe (2) e

+
2+ - 3+ 2+
4 2
5Fe MnO 8H 5Fe Mn 4H O
+
+ + + +
(
)
x 5
6
Cn bng phn ng oxy ha - kh
2+ 2- 3+ 3+
2 7
Fe Cr O Fe Cr + +
2- - 3+
2 7
Cr O e ? Cr +
2+ 2- 3+ 3+
2 7 2
6Fe Cr O 14H 6Fe 2Cr 7H O
+
+ + + +
7
3. Chiu ca phn ng oxy ha- kh
Mch in oxy ha-kh
2+ 4+ +3 3+
Fe Ce Fe Ce + +
Fe
2+
b oxy ha
(in cc anode)
Ce
4+
b kh
(in cc cathode)
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.
-(Pt
I
) Fe
2+
Fe
3+
Ce
3+
Ce
4+
(Pt
II
)+
8
- Zn(s) , Zn
2+
(aq) || Cu
2+
(aq) , Cu(s) + E
cell
= 1.103
Zn Zn
2+
+ 2e
- Cu
2+
+ 2e
-
Cu
9
4. Th oxy ha- kh
in cc hydro chun (SHE)
2 H
+
(a = 1) + 2e
-
H
2
(g,1atm)
Pt|H
2
(g,1atm)| 2H
+
(a = 1)
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)
Qui c: E = 0 V
10
Th chun
Pt|H
2
(g, 1 atm), H
+
(a = 1) || Cu
2+
(1 M), Cu(s) E
cell
= ?
E
cell
= E
cathode
- E
anode
E
cell
= E
Cu
2+
/Cu
- E
H
+
/H
2
0.340 V = E
Cu
2+
/Cu
- 0 V
E
Cu
2+
/Cu
= +0.340 V
H
2
+ Cu
2+
H
+
+ Cu(s) E
cell
= 0.340 V
cathode
anode
11
cathode
cathode anode
anode
o th chun
H
2
2H
+
+ 2e
-
Cu
2+
+ 2e
-
Cu 2H
+
+ 2e
-
H
2
Zn Zn
2+
+ 2e
-
E
0
Cu2+/Cu
= 0,34 V
E
0
Zn2+/Zn
= -0,763 V
12
th o c vi in cc hydro chun khi nng ca
cc ion = 1M, nhit 25
0
C gi l th chun (E
0
)
(Pt) H
2
, 2H
+
|| Fe
2+
, Fe
3+
(Pt)
S mch Galvanic ca st clorua vi in cc hydro
hiu s th trn cc cc ca mch galvanic = +0,771 V
Gi tr dng ch tnh oxy ha ca Fe
3+
> H
+
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
4+ 3+ 0
Ce Ce E 1,61V e + =
2+ 0
Zn 2 Zn E 0,76V e + =
Ce
4+
l tc nhn oxy ha mnh, Ce
3+
tc nhn kh yu
Zn
2+
l tc nhn oxy ha yu, Zn tc nhn kh mnh
SHE|| Fe
2+
, Fe
3+
(Pt) hay
13
TH CHUN
Bn phn ng
F
2
+ 2e
-
2F
-
MnO
4
-
+ 5e
-
Mn
2+
Ce
4+
+ e
-
Ce
3+
(in HCl)
O
2
+ 4H
+
+ 4e
-
2H
2
O
Ag
+
+ e
-
Ag(s)
Cu
2+
+ 2e
-
Cu(s)
2H
+
+ 2e
-
H
2
(g)
Cd
2+
+ 2e
-
Cd(s)
Fe
2+
+ 2e
-
Fe(s)
Zn
2+
+ 2e
-
Zn(s)
Al
3+
+ 3e
-
Al(s)
K
+
+ e
-
K(s)
Li
+
+ e
-
Li(s)
E
o
(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
T

n
h
o
x
y

h

a
t

n
g
T

n
h
k
h

n
g
Tc nhn
Oxy ha
Tc nhn
kh
14
Sc in ng ca pin
- (Pt
I
) Sn
2+
, Sn
4+
Fe
3+
, Fe
2+
(Pt
II
) +
cathode anode
pin right left cathode anode + -
E E E E E E E = = =
3+ 2+ 4+ 2+
0 0
pin
Fe /Fe Sn /Sn
E E E
0, 771 0,154 0, 617
=
= =
4+ 2+
3+ 2+
4+ - 2+ 0
Sn /Sn
3+ - 2+ 0
Fe /Fe
Sn 2e Sn , E 0,154
Fe e Fe , E 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)
* Khi pin c thit lp, s ca pin lun dng
15
Tnh sc in ng ca pin c thit lp t 2 bn pin sau
3+ 2+ - -
3
0 0
Fe /Fe I /I
E E E 0, 771 0, 536 0, 235
pin
= = =
3+ 2+ 0
- - 0
3
Fe Fe E 0,771V
I 2 3I E 0,5355V
e
e
+ =
+ =

3+ 2+ - -
3
0 0
Fe /Fe I /I
vi E E >
3+ - 2+ -
3
2Fe 3I 2Fe I + = +
16
5. Phng trnh NERNST
[ ]
[ ]
a
O
b
Ox
0.05916
E E log
n Kh

= +



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

= +



E
o
= 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 10
4
C/mol
n = s in t
Mt dd gm Cr
2
O
7
2-
10
-3
M v Cr
3+
10
-2
M. Tnh th ca bn
pin trong mi trng acid pH = 2
2- 3+
2 7 2
Cr O 14H 6 2Cr 7H O e
+
+ + +
7
2- 3+
Cr O /Cr
2
7
2- + 14
2
0
2
3+
[Cr O ][H ]
0.05916
E E log 1.06V
6
Cr


= + =




17
5. Phng trnh NERNST
Cho pin Cu Fe iu kin chun (nng = 1M)
Cu
2+
+ 2e
-
Cu(s) 0.339 V
Fe
2+
+ 2e
-
Fe(s) -0.440 V
Xt ton b phn ng: Th ca ton phn ng
pin + -
E E E =
0 0 0
& E E E
pin +
=
Phn ng Galvanic
Cu
2+
(aq) + Fe(s) Cu(s) + Fe
2+
(aq)
Fe|Fe
2+
(1M) || Cu
2+
(1 M)|Cu
0 0 0
E E E 0, 339 0, 440 0, 779V
pin +
= = + =
2 1 1 2 1 2 2 1
Ox Ox n n Kh n n Kh + +
1 2
2 1
0 0 0 2 1
pin + -
1 2 1 2 1 2
[Ox ] [Kh ] 0.05916 0.059
E (E E ) lg lg
[Ox ] [Kh ]
n n
n n
E Q
n n n n
= =
18
(Pt) Fe
2+
(0.10 M),Fe
3+
(0.20 M)||Ag
+
(1.0 M)|Ag(s)
p dng phng trnh Nernst tnh s ca pin sau, E
pin
.
E
pin
= E
pin
- log Q
n
0.05916
E
pin
= E
pin
- log
n
0.05916 [Fe
3+
]
[Fe
2+
] [Ag
+
]
Fe
2+
(aq) + Ag
+
(aq) Fe
3+
(aq) + Ag (s)
E
0
pin
= 0.799 V 0.771 V = 0.0280
E
pin
= 0.028 V 0.018 V = 0.010 V
19
5. Phng trnh NERNST
Phn ng Galvanic
Fe|Fe
2+
(1M) || Cu
2+
(1M)|Cu
Cu
2+
(aq) + Fe(s) Cu(s) + Fe
2+
(aq) E
pin
= 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
E
pin
0 : l do ht pin
E = 0 p.ng ca pin t cn bng
20
5. Phng trnh NERNST- Th cn bng
Khi pin t n cn bng ( 25
0
C) : E
pin
= 0
E
0
> 0: K > 1
E
0
< 0: K < 1
o
1
2
n n E /0.05916
K 10 =
1 2
2 1
0 0 0 2 1
pin + -
1 2 1 2 1 2
[Ox ] [Kh ] 0.05916 0.05916
E (E E ) lg lg 0
[Ox ] [Kh ]
n n
n n
E Q
n n n n
= = =
0
pin
1 2
0.05916
E lg 0 E K
n n
= =
21
G
0
K
cb
E
pin
0
pin
RT
E lnK
nF
eq
=
0
G RTlnK
eq
=
0 0
G =H-TS
0 0
pin
G nFE =
H
0
S
0 0
pin
E , E
o thnh
phn cb
Mi quan h gia nhit ng hc (G
0
), cn bng (K
cb
)
v in ha hc
22
6. in cc so snh (Reference Electrode)
in cc bc (Ag/AgCl)
bo ha bng dd KCl
AgCl(s) + e
-
Ag (s) + Cl
-
E = +0.197 V
in cc calomel (SCE)
bo ha bng dd KCl
Hg
2
Cl
2
+ e- Hg + Cl
-
E = +0.241 V
23
6. in cc so snh
E
o
= E
o
- 0.241 (SCE)
E
o
= E
o
- 0.197 (Ag/AgCl)
E
o
(SHE)
E
(SCE)
E
(Ag/AgCl)
Cu
2+
+ 2e
-
Cu(s) 0.339 V 0.098 V 0.142 V
Fe
2+
+ 2e
-
Fe(s -0.440 V -0.681 V -0.637 V
24
7. Chun oxy ha 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 HNO
3
.
2+ 4 3+ 3+
Fe Ce Ce Fe
+
+ +
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
3+ 2+
4+ 3+
0
Fe /Fe
0
Ce /Ce
E 0,771V
E 1,61V
=
=
25
2+ 4 3+ 3+
Fe Ce Ce Fe
+
+ +
Phn ng chun :
Thm V =10,0 mL Ce
4+
2+ 2+ 4+ 4+
Fe Fe Ce Ce
V M V M >
# mmol Ce
4+
thm vo = 0,100M x 10,0 mL = 1.00 mmol
# mmol Fe
3+
to thnh = 1.00 mmol
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 HNO
3
.
# mmol Fe
2+
cn li = (0,100 M x 100,0 mL)-1,00 mmol = 9,00
3+ 2+
3+
0
2+ Fe / Fe
0, 0592 [Fe ]
E E log
[Fe ] n
= +
E 0, 771 0, 0592log(1, 00/ 9, 00) 0, 714V = + =
26
2+ 4 3+ 3+
Fe Ce Ce Fe
+
+ +
Phn ng chun :
Thm V =50,0 mL Ce
4+
2+ 2+ 4+ 4+
Fe Fe Ce Ce
V M V M >
# mmol Ce
4+
thm vo = 0,100M x 50,0 mL = 5.00 mmol
# mmol Fe
3+
to thnh = 5.00 mmol
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 HNO
3
.
# mmol Fe
2+
cn li = (0,100 M x 100,0 mL)-5,00 mmol = 5,00
3+ 2+
3+
0
2+ Fe / Fe
0, 0592 [Fe ]
E E log
[Fe ] n
= +
5, 00
E 0, 771 0, 0592log 0, 771V
5, 00
= + =
27
2+ 4 3+ 3+
Fe Ce Ce Fe
+
+ + Phn ng chun :
Thm V =100,0 mL Ce
4+
2+ 2+ 4+ 4+
Fe Fe Ce Ce
V M V M =
# mmol Ce
4+
thm vo = 0,100M x 100,0 mL = 10,0 mmol
# mmol Fe
3+
cb = 10,0 x ~ 10,0
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 HNO
3
.
# mmol Ce
3+
cb = 10,0 x ~ 10,0
# mmol Fe
2+
cb = x
# mmol Ce
4+
cb = x
im tng ng
28
2+ 4 3+ 3+
Fe Ce Ce Fe
+
+ + Phn ng chun :
Thm V =100,0 mL Ce
4+
2+ 2+ 4+ 4+
Fe Fe Ce Ce
V M V M =
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 HNO
3
.
im tng ng
3+ 2+ 4+ 3+
Fe /Fe Ce /Ce
E E =
3+ 2+ 4+ 3+
3+ 4+
0 0
2+ 3+ Fe / Fe Ce /Ce
0, 0592 [Fe ] 0, 0592 [Ce ]
E log E log
[Fe ] [Ce ] n n
+ = +
3+ 2+ 4+ 3+
3+ 3+
0 0
2+ 4+ Fe / Fe Ce /Ce
0, 0592 [Fe ] [Ce ]
E E log 0, 0592log
1 [Fe ] [Ce ]
cb
K = =
14
1, 7 10
cb
K x =
29
2+ 4 3+ 3+
Fe Ce Ce Fe
+
+ + Phn ng chun :
Thm V =100,0 mL Ce
4+
2+ 2+ 4+ 4+
Fe Fe Ce Ce
V M V M =
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 HNO
3
.
im tng ng
3+ 2+ 4+ 3+
Fe /Fe Ce /Ce
E E =
3+ 3+
14
2+ 4+
[Fe ] [Ce ] (10, 0)(10, 0)
1, 7 10
[Fe ] [Ce ] ( )( )
cb
K x
x x
= = =
7 2 4
7, 7 10 x x mmol Fe mmol Ce
+ +
= =
3+ 2+
0 3+ 2+
Fe / Fe
7
E E 0, 0592log[Fe ] /[Fe ]
0, 771 0, 0592log(10, 0/ 7, 7x10 ) 1,19V

= + =
= + =
30
2+ 4 3+ 3+
Fe Ce Ce Fe
+
+ + Phn ng chun :
Thm V =100,0 mL Ce
4+
2+ 2+ 4+ 4+
Fe Fe Ce Ce
V M V M =
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 HNO
3
.
im tng ng
3+ 2+ 4+ 3+
Fe /Fe Ce /Ce
E E E
cb
= =
3+ 2+
4+ 3+
3+
0
cb
2+ Fe / Fe
4+
0
cb
3+ Ce /Ce
[Fe ]
E E 0, 0592log
[Fe ]
[Ce ]
E E 0, 0592log
[Ce ]
= +
= +
3+ 2+ 4+ 3+
3+ 3+
0 0
cb 2+ 4+ Fe / Fe Ce /Ce
[Fe ][Ce ]
2E (E E ) 0, 0592log
[Fe ][Ce ]
= +
31
2+ 4 3+ 3+
Fe Ce Ce Fe
+
+ + Phn ng chun :
Thm V =100,0 mL Ce
4+
2+ 2+ 4+ 4+
Fe Fe Ce Ce
V M V M =
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 HNO
3
.
im tng ng
3+ 2+ 4+ 3+
Fe /Fe Ce /Ce
E E E
cb
= =
3+ 2+ 4+ 3+
3+ 3+
0 0
cb 2+ 4+ Fe / Fe Ce /Ce
[Fe ][Ce ]
2E (E E ) 0, 0592log
[Fe ][Ce ]
= +
Ti cb
3+ 4+ 3+ 2+
[Fe ] [Ce ] & [Ce ] [Fe ] = =
3+ 2+ 4+ 3+
0 0
cb
Fe / Fe Ce /Ce
1
E (E E ) 1,19
2
V = + =
32
2+ 4 3+ 3+
Fe Ce Ce Fe
+
+ +
Phn ng chun :
Thm V = 200,0 mL Ce
4+
2+ 2+ 4+ 4+
Fe Fe Ce Ce
V M V M <
# mmol Ce
4+
thm vo = 0,100M x 200,0 mL = 20.0 mmol
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 HNO
3
.
# mmol Ce
4+
d = 20,0 -(0,100 M x 100,0 mL) = 10,0 mmol
4+ 3+
4+
3+ Ce / Ce
0, 0592 [Ce ]
E E log
[Ce ] n
= +
10, 0
E 1, 61 0, 0592log 1, 61V
10, 0
= + =
# mmol Ce
3+
to thnh = 10,0 mmol
33
34
2+ - + 3+ 2+
4 2
5Fe MnO 8H 5Fe Mn 4H O + + + +
Phn ng chun :
Tnh th ti im tng ng ca qu trnh chun
100,0 mL dd Fe
+2
trong dd H
2
SO
4
0,500M bng 100,0 mL
dd MnO
4
-
0,0200 M.
4+ 3+
2+
4
0
Fe / e
0
/
E 0, 771
E 1, 51
F
Mn MnO
V
V

=
=
35
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
Ch th h tinh bt
Vi d: Chun KMnO
4
(mu tm)
Vi d: Chun Iod, ho tinh bt to phc vi I
2
xanh m
Ch th oxy ha kh
Cht c mu thay i tu thuc vo th oxy ha kh
36