.

, , .
,






:

.
-1
-2,
(..
22) -1
+1,
(.. CaH2, LiH) -1
4



2Fe3+ + Sn2+ 2Fe2+ + Sn4+
Fe3+ ,
(3+ 2+)
Sn2+ ,
(2+4+)
,




22 + 2+ + 2e- 2H2O ( )
Ag Ag+ + e- ( )
2Ag 2Ag+ + 2e22 + 2+ + 2Ag 2Ag+ + 2H2O ( )


:
) ,
-

) ,


( )
(
). , ,

7

:
) , (, +)
(, -)
) ,

e-

(-),
Na+
(- *)
* 801C

NaCl, :
(+),
Cl- Cl2 ( )

e-

 Downs
Na
NaCl.
Na

Cl2
Na(s)+Cl2(g)

10

 NaCl
NaCl
:
, Cl Cl2
,
H2O 2(g) -

 Na2SO4
Na2SO4
!
(+), 2
2(g) +
(-), H2O
2(g) -

12

 Faraday
M. Faraday (1791-1867)




Faraday
1 mol
1F = (6,022x1023) x (1,6x10-19)= 96485 Coulomb

13


(STP)
. (: Ia=2,5 amperes t=50 min)
() 2 :
22 O2 + 4H+ + 4e2mol

1mol=22.4L

4mol = 4x(9,65x104) C

: C=Iat
C = (2,5 A) x (50 x 60 s) = 7,5x103 C
, LSTP O2= 7,5x103 C x 22,4 L / [4x(9,65x104 C)] = 0.435 L

14


:
MnO4-(aq) + C2O42-(aq) MnO2(s) + CO32-(aq)
( )

15


:
(+),
Ag(s) Ag+(aq) + e(-),
Ag+(aq) + e- Ag(s)

16

:
)
) (
)
Daniel:
(-): Zn(s) Zn2+(aq) + 2e(+): Cu2+(aq) + 2e- Cu(s)
ZnZn2+ (1M)Cu2+ (1M)Cu
17

Cu

 Cu-Ag
- :
(-): Cu(s) Cu2+(aq) +2e(+): 2Ag+(aq) + 2e- 2Ag(s)
Cu(s) + 2Ag+(aq) Cu2+(aq) + 2Ag(s)

Cu Cu2+ (1M)Ag+ (1M) Ag
18


Zn2+ < Cu2+ < Ag+

g < Cu < Zn

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

19

O Cu

Ag
O Zn

Cu



Cr 1 Cr(NO3)3 Ag
1 AgNO3. Cr
Ag.
Ag+(aq) + e- Ag(s)
(, )
Cr(s) Cr3+(aq) + 3e- (, )
-----------------------------------------------------------------------------------Cr(s) + 3Ag+(aq) Cr3+(aq) + 3Ag(s)
Cr(s)Cr3+(aq)Ag+(aq)Ag(s)
20



(-)



Eo 0 V. (Eo 25 C, 1
M 1 atm)

21

Pt,H/H+


:
Hg2Cl2(s) + 2e- 2Hg(l) + 2Cl-(aq) (Eo= 0.268 V)
1 KCl,
Eo= 0.273 V (25 C)

KCl, Eo= 0.242 V (25 C).
Pt
Hg2Cl2(s)

22

Hg/Hg2Cl2/Cl-(aq)

Hg(s)
Cl

 Zn-SHE
+ =

SHE 0 V,
(E0)
0,763 V, E0 (Zn)
0,763 V

ZnZn2+(1M)H+(1M); H2(1atm)Pt

23


Zn SHE,
:
Zn Zn2+ + 2e- (Eo= +0,763 V, )
Zn2+ + 2e- Zn (Eo= -0,763 V, )

(.. Zn2+ + 2e- Zn).
SHE.
Eo > 0 vs. SHE ()
Eo < 0 vs. SHE ()
24

25

 -




( !)

.
, ,
, cell
cell
26


Cr, Cr3+(1)
Cu, Cu2+(1) , Eo,

Cu Cr. ,
3(Cu2+ + 2e- Cu)
()
Eo= +0,337 V
2(Cr Cr3+ + 3e-)
()
Eo= +0,74 V
---------------------------------------------------------------------------------------------------2Cr + 3Cu2+ 2Cr3+ + 3Cu
Eo= +1,08 V
, Cu2+ Cr Cr3+
Cu

27

28


Pt/Sn4+(1M), Sn2+(1M)
Pt/NO3-(1M),NO (1 atm) ocell
3-/ , ,
. Sn4+/Sn2+ :

Sn2+ Sn4+

29

 2
2H2O(l) + 2e-

Ca(s)

30

H2(g) + 2OH-(aq) E0= -0.42 V

A dental voltaic cell

Al3+ + 3eO2 + 4H+ + 4e-

Al

Eo = -1.66 V
2H2O Eo= 1.23 V

Al(s) ,
,
Ag/Sn/Hg .

( ).

31



, 2,
, :

4Fe2+ + O2 4Fe3+ + 2O2-

32



(.. Sn Fe, )

(n, Ni, Cr MgFe)

(.. Al2O3)
, Pb3O4, o
Fe

33



. Zn ,
()
() .

34


~10.000

Eiffel

7
50-60
( PbOxSiO2).

35


Nernst
( 1 / 1atm /
25oC)

, (V), R
(8.314 J/molK), (), n mol
, F
Faraday (96485 J/Vmol e-), Q= ,
([]/[])
36


Fe3+/Fe2+
Fe2+
Fe3+
H :
Fe3+ + e- Fe2+ (Eo= 0,771 V)
Q = [Fe2+]/[Fe3+] = 5 n = 1

0,0592
0,0592
E =E
log Q = 0,771
log 5 = 0,730 V
n
1
o

37


( Q) :
Fe2+(aq) + Ag+(aq) Fe3+(aq) + Ag(s)
(-): Fe2+ Fe3+ + e- (Eo()= -0,771 V)
(+): Ag+ + e- Ag (Eo()= 0,799 V)
Eo = Eo() + Eo() = 0,799-0,771 = 0,028 V
=0. ,
log Q= 0,028/(0,0592/1) = 2,97

38

25 C

0,0592
log Q
E =
n
o



Fe3+(1M)/ Fe2+(0.1M) MnO4(0.01M)/Mn2+(110-4M) [+]= 110-4M.
:

39

40



Cl2(0.1atm)/Cl-(0.1M) MnO4-(0.1M)/ Mn2+(0.1M)
[+]= 0.1M.
: MnO4- + 8H+ + 5e- Mn2+ + 4H2O (Eo= 1,507 V)
Cl2 + 2e- 2Cl- (Eo= 1,360 V)

41


Nernst
[+]
ZnZn2+(1M)H+,H2(1atm)Pt = 0,522 V 25 oC
H :
Zn + 2H+ Zn2+ + H2 (Eo= 0,763 V)

42


,
,

pH=0

Latimer

:
Eo > 0,8 V ( )
Eo ~ 0,8 V ( )
Eo < 0,8 V ( )
43


(disproportonation)

..

(? E0=0,37 V)
Cu+(aq) + e- Cu(s) (Eo= 0,52 V)
Cu2+(aq) + e- Cu+(aq) (Eo= 0,15 V)

44


(G)

(0>0)
(G<0)
G
:
G = nFEo()
G ( )

G , G = 0

45



:
G = RlnK
,
o
, RTlnK = nFEo
nFE
ln K =
RT
:
> 0
G < 0
K>1

46


Fe3+
.

(G0 = G01 + G02)

Fe3+ Fe
Eo Fe3+ Fe2+ Fe2+ Fe!
( = -0,04V)
47


25 C

2Cu + PtCl62- 2Cu+ + PtCl42- + 2Cl-

48

 : Leclanch

Daniel ( )
Leclanch Zn ((-))
((+)).
MnO2, 4Cl ZnCl2 ,

49


Pb PbO2
20% .

50

 - (Ni-MH)

51

 -

H2 2 H2O.
- ,
.

(PAFC)
(DMFC)
52


Zn

Cu

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

53


Mn2+ 2
pH=0, 2
[-]=1
:
Mn3+(aq) + e- Mn2+(aq) (Eo= 1,54 V)
O2(g) + 4H+(aq) + 4e- 2H2O(l) (Eo= 1,23 V)
Mn(OH)3(s) + e- Mn(OH)2(s) + OH- (Eo= 0,18 V)
O2(g) + 2H2O(l) + 4e- 4HO-(aq) (Eo= 0,40 V)

!

54


G (298K) mol
Mn3+ :
4Mn3+(aq) + 2H2O(l) 4Mn2+(aq) + O2(g) + 4H+(aq)
:
Mn3+(aq) + e- Mn2+(aq) (Eo= 1,54 V)
O2(g) + 4H+(aq) + 4e- 2H2O(l) (Eo= 1,23 V)
(G0= 21 kJ/mol Mn3+)

54