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C . ,

: - (, ) - - - -

1


7.1 ­ 7.4

; ;
.., 1927: (q = 0)



d =-


i

( i d i )

()

q = -F


i

( zi i )



dq C= dE



d = + d ln s



2


7.3 ­ 7.5




d =- qdE -



i

( i d i )

= -q E ai



, E; , ai
C , E; C , ai


q, E; q, ai i , E ; i , ai
dU dI =R dt dt dE dU = - dt dt I +; C dI R = v = const dt
3






7.3


NaF Na2SO4
( ) ,-



4


7.2, 7.3



- (1', 2') ( 2')

- (1, 2)

( )
5


7.4




C ( );

6


7.11 ­ 7.12



d 2 F =- 2 dx 0

-


i

zi F ( x) c z exp - RT
(0 ) i i

., 1910, ., 1913: ­

1,1-

d 2 =- 0 dx 2

d 2 2 Fc F =- sh 2 dx 0 RT


q = dx
x2



F 2 q =-2 2 RT 0 c sh 2 RT

2





2 exp( - x )



-1

- ( )
7




- - ,
8


7.11 ­ 7.14



., 1853

C = 0 / d


- . , 1924

1 1 1 = + C C


C



=

F 4 A2 c + q 2 RT

2

=

max



( E )c =


1-



exp(-2a )
9




10


(111)

Au

Au(111)

... Ag(100)

11




Au(111)

12


- (Atomic Force Microscopy, AFM)

13




14


.

, In situ - - - - - - Ex situ - -

15


7.5, 7.6



( ): H3O+ + e(Pt) = Pt_Had + H2O

Q =q ± F Ai


dE =

d

H

+

F

d - F

H

d =- H d H - H + d
: ( )

H

+

-

i H ,H



+

i d

i

Q = const iv

Ai ( E )

16

Q = I it










( Q )

Pt(110)

Pt(111)

17


7.2

( )

: - 30 /2; - 200-400 /2

1 2 1




18










19


7.6

-
Underpotential deposition (upd) ­ H upd Cu2+/Cu «» 0
+

O upd: H2O ­ 2e = 2H+ + O (RHE), V 1.23
a

u upd: Cu

2+

+ 2e = Cu

a

Ag /Ag

Ag upd: Ag+ + e = Ag

RHE ­ reversible hydrogen electrode ( )

20


u upd



u

21




CF3COOH HF




22


/

IrO2 Fe2O2 Al2O2 FeO(OH)

cassiterite

TiO2

23


7.7

In situ
Furier-transformed infrared spectroscopy (FTIRS) ­ - - Electromodulation infrared spectroscopy (EMIRS) ­ Subtraction normalized infrared spectroscopy (SNIFTIRS) ­ c 200 ­ 4000 -1 - : - second harmonic generation (SHG) ­ ; - surface enhanced Raman scattering (SERS) ­ ()

350 ­ 800


24


7.8, 7.9

in situ
STM ­ scanning tunneling microscopy ( ) AFM ­ atomic force microscopy (- ) EXAFS ­ extended X-ray absorption fine structure ( ) XANES ­ X-ray absorption near edge structure ( ) **************************** XRD, ND ­ X-ray and neutron diffraction ( ) DEMS ­ differential electrochemical mass-spectroscopy ( -) EQCM (EQCN) ­ electrochemical quartz crystal micro(nano)balance (25 - )


In situ : ( )

7.8

:

26


Butterfly ­ Pt(111)

H2SO4:

27


Modern Aspects of Electrochem. V. 36(2003), p.51-130

Ab initio

: tsir@elch.chem.msu.ru
28