2

LOGO

(Electrochemistry)
(Electrochemistry)



..


www.science.mju.ac.th/chemistry/

3 4
9.1 (Redox reaction) .
- 2
() (
)

(oxidation number) (oxidation state)
= ()
2
= ( Ox )
.
= ( Ox )
.
Ox = Re =
 5 6

Zn ()
Re =

Cu2+ ()

7 8
.

(EN)
EN
EN

1. 0 He, Na, O2, O3
= 0
2. Na+
=+1, Mg2+=+2, O2-=-2, Cl-=-1
 9 10

3. ( 1A) 6. -2
= +1 NaCl, K2SO4, Li3PO4 (Na, K, Li H2O, NaOH, H3PO4 (O=-2)
=+1) -1 H2O2, Na2O2, BaO2
4. ( 2A) OF2 +2
= +2 CaCl2, Mg3(PO4)2, BaSO4 (Ca, Mg, 7.
Ba =+2) =
5. +1 KMnO4 = O => K =+1, O=-2x4=-8
H2O, Ca(OH)2, H2SO4 (H =+1) Mn + 1 + (-8) = 0
Mn = +7

11 12
9.2 9.2.1

1.
2.
(
)
2
3. (
9.2.1 )
9.2.2 2 4.

 13 14

5. 1 ()
6. Cu + HNO3 Cu(NO3)2 + NO + H2O
, 2
, 0 +5
Cu + HNO3
+2 +2
Cu(NO3)2 + NO + H2O

1
Cu + HNO3 Cu(NO3)2 + NO + H2O

15 16

3 2

1 ()
4 2

5 6
 17 18

3 5
Cu2S + 14HNO3 2Cu(NO3)2 + H2SO4 + 10NO2 + 6H2O
6

4

+4HNO3 4NO3-

Cu2S + 14HNO3 2Cu(NO3)2 + H2SO4 + 10NO2 + H2O

19 20
9.2.2
2 3
1.
e-
2.
H+ OH-
3. O, H H2O 1
4. ()

5.

 21 22

2 4
()

( H+ ) 5

3 ()
7H2O

23 24

4 2
OH-

OH-

1 3 O, H H2O


 25 26

4
3

2

5

27 28
9.3 (Electrochemical cell)


2 2
. (Chemical cell) 1. (Galvanic cell)
. (Electrolytic cell) 2. (Concentration cell)

Anode Cathode
() ()
 29 30
9.3.1

(Zn)
(Cu)

Anode Cathode
Zn Cu

Net: Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

31 32
9.3.1.1
4.
1. Cu(s)|Cu2+(0.1M)||Ag+(0.1M)|Ag(s)
(|) 5. |
Zn(s)|Zn2+(x M)
2. Pt(s)|H2(g, 1 atm)|H+(aq)
(|) 6.
Cu2+(y M)|Cu(s)
3. || Zn(s)|Zn2+(xM)||Cu2+(yM)|Cu(s) Fe(s)|Fe2+(aq),Fe3+(aq)||Cu2+(aq)|Cu(s)
 33 34
9.3.1.2

1. 1 M
2. 1 atm
3. 25 oC

4. = 0 V

35 36

Eo Zn(s)|Zn2+(1M)
(Standard Hydrogen Electrode: SHE)

() E0cell E0cathode E0anode
1 M
E0cell E0 E0
25C H H2 Zn Zn2
1
0.76 V 0 E0
Zn Zn2
2H+(aq) + 2e- H2(g)
Zn(s)|Zn2+(1 M)||H+(1 M)|H2(1 atm)|Pt(s)
E0 0.76 V

= 0.76 V Zn Zn2
0.00 V E H2 = 0.00 V
Pt(s)|H2(g,1 atm)|H+(aq,1 M)
 37 38

Eo Cu(s)|Cu2+(1M) Eo
1. e-
2. Ox
3. e- H+
E0cell E0cathode E0anode 4. E0
5. Re
E0cell E0 2 E0
Cu Cu H H2 6.
(Eo )
0.34 V E0 0 (Eo )
Cu Cu2
Pt(s)|H2(1 atm)|H+(1 M)||Cu2+(1 M)|Cu(s) 7.
Eo
E0 0.34 V
= 0.34 V Cu Cu2 8. Eo
9.

39 40
(Nernsts equation)
(E) 1 M Fe2 (aq) Cd(s) Fe(s) Cd2 ( aq )

[Fe2 ] 0.60 M [Cd2 ] 0.010 M E 298 K n 2
Cu2 Zn Cu Zn2

Fe2 2e - Fe( s ) E0 -0.44 V
0 RT
E E ln Q R=8.314 J K-1 mol-1 Cd2 2e - Cd( s ) E0 -0.40 V
nF
2.303RT T=K=273+oC E0 E0 (Fe2 ) - E0 (Cd2 )
E E0 log Q
nF n=Number of electron -0.44 V - (-0.40 V)

[Zn2 ] F=96487 J V-1 mol-1 -0.04 V

Q 0.0592 [Cd2 ]
[ Cu2 ] E E0 log 2
n [Fe ]
2.303RT [Zn2 ] 0 0.0592 [Zn2 ]
E E0 log 2 E log 2 0.04 V
0.0592 [0.010]
log 0.013 V E
nF [ Cu ] n [ Cu ] 2 [ 0.60]
 41 42
(Concentration cell)
2 Zn(s)|Zn2+(0.1 M||Zn2+(1.0 M)|Zn(s)
E0
0.0592 [0.1]
log
Anode Cathode
2 [1.0]
Zn Salt bridge
Zn =0.0296 V

E0 = 0 V
(Ksp) Zn2+ (0.1 M) Zn2+ (1.0 M)
AgCl, BaSO4, CaCO3
Zn(s) Zn2+(0.1 M) + 2e- Zn2+(1.0 M) Zn(s)

43 44
9.3.1.3 : ()
2 ()
()
NH4Cl, ZnCl2, MnO2


1. Anode (Oxidation) Zn(s) Zn2+(aq) + 2e-

2. Cathode (Reduction) 2MnO2(s) + 2NH+4(aq) + 2e- Mn2O3(s) + H2O(l) + 2NH3(g)
Zn(s) + 2MnO2(s) + 2NH+4(aq) Zn2+(aq) + Mn2O3(s) + H2O(l) + 2NH3(s)
-
Zn2+(aq) NH3(g) [Zn(NH3)4]2+ (aq)
-
1.5 V

 45 46
:

( PbO2)
H2SO4
( Pb)

( Pb) PbSO4 PbO2
Pb 2

( PbSO4)

( PbSO4)
( PbO2)
+

47 48
9.3.2


1. 1.
E0 2. 2.

3. 3.
1.
2. 4. 4.
3.
 49 50

, G Ecell

G Ecell

<0 >0

>0 <0

51 52
9.3.2.1
MX
MX(s) M+(aq) + X-(aq)
()
()

E01> E02 M+ e- H2O M(s)

E03> E04 X- e- H2O
X2(g)
 53 54
9.3.2.2
CuSO4 2
Na+
()
Na(s)
() Cl-
Cl2(s)
O2 E0 H2O E0 SO42-
Cu E0 Cu2+ E0 H2O 2Cl- Cl2 + 2e-(aq) E0 = -1.36 V
Na+(aq) + e- Na(s) E0 = -2.71 V
2Na+(aq) + 2Cl-(aq) 2Na(s) + Cl2(g) E0cell = -4.07 V

55 56
9.3.2.3 9.3.2.4

()
: () ()
: ()

:
: Cu(s) Cu2+(aq) + 2e-
Fe(s) Fe2+(aq) + 2e-
Zn(s) Zn2+(aq) + 2e-
Ag(s) Ag+(aq) + e- Cu2+(aq) + 2e- Cu(s)
Ag+(aq) + e- Ag(s)

Ag, Au, Pt E0 Cu
 57 58
9.3.3


1 (96,487 C) 1/n
Cu2+ + 2e- Cu 1 Cu
Anode : Fe(s) Fe2+(aq) + 2e-
31.75
Cathode : O2(g) + 2H2O(l) + 4e- 4OH-(aq)
Al3+ 27 : 2Fe(s) + O2(g) + 2H2O(l) 2Fe2+(aq) + 4OH-(aq)
: 4Fe2+(aq) + O2(g) + (4+2n)H2O(l) 2Fe2O3.nH2O(s) + 8H+(aq)
E0
Al3+ + 3e- Al 3
() Mg Mg e- Mg
3 x 96,487 C = 289,461 C Al 27 e- O2

59
LOGO

1. O2 H2O

2. (stainless steel)
3. Zn, Cr, Sn
Zn ()
H2O O ZnO
4. E0 Cathodic
protection