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.

(wasq@elch.chem.msu.ru)

http://www.elch.chem.msu.ru/rus/prgfnm.htm



i = i - i
s cO i = i0 i = i0 1

9.4

,
s cR (, t ) - c 0 exp R

(, t ) nF exp 0 cO RT

(1 - ) nF - RT



i0
i0 = 0.02id

i i nF - ( O ) exp - 1 + ( R ) exp id RT id
(O ) d

(1 - )nF - RT
O)

i0 << i

i i = i 1 - (O ) id
R)

i=

( iid

( idO ) - i

RT ( ( | |<< ; i << idO ) ; id nF

nF i i -( -( i i0 RT idO ) id R )

RT i nF

1 1 1 + (O ) + ( R ) id i0 id

· (, ) · · · ..




9.3

m F i = i0 exp + - exp RT



n-m F - - RT

F c (1 - 1 ) F i = 2i01 exp 1 - X exp - 0 = 2i02 RT c X RT
( + 2 ) F (2 - 1 - 2 ) F - exp - exp 1 RT RT i=2 1 F 1 (1 - 1 ) F + exp - exp 2 i01 RT RT i02

cX F (1 - 2 ) F exp 2 - exp - 0 RT RT cX
· . · ( )



A + B O R
e
-

10.1

O R A + B
e

-



H3O+ + e­ H H




+ H2O ( ) 2H H2 ( )

+ H3O+ + e­ H2 + H2O ( )



O2 2O O O




O2 + 2H+ + 2e­ H2O
­

2

O2 + e­ O
­

2

­

+ 2H+ + 2e­ H2O + H2O + 2e­ 2OH

H2O2 + 2H+ + 2e­ 2H2O O2 + H2O + 2e­ OH­ + HO HO2­ + H2O + 2e­ 3OH
­ 2

O2­ + H3O+ HO2 + H2O HO2 + e­ HO2
­

HO2­ + H3O+ H2O2 + H2O





p v = v - v = k R - k p R

10.1

i = nFv0 i0

p R - 1 R

=

RT i ln 1 + pnF i0

RT n F 2 R
2

max =

Rs =

RT n 2 F 2 R 2 +2

=

v0 p R
Electrochimica Acta 20 (1975) 913-916

1 RT =22 Cs n F R 2 + 2



.

10.2

k1 = 0

k1 = 0.2

k1 = 2

(k1 = const)


()

BASi DigiSim® Simulation Software for Cyclic Voltammetry



http://www.basinc.com/products/ec/digisim/
V. Mazine, J. Heinze, J. Phys. Chem. A 2004, 108, 230-235




k

10.5

ik =


k

ik



4 3 RT c* A =- G = 4r - r ln 3 Vm c
2

10.6

( )


2.0

-1.2 -1.0 -0.8 I, /
2

1.5

1.0

I,mA

0.5

-0.6 -0.4 -0.2 0.0

-0.225 -0.2 , -0.1 , -0.1 ,

, 70 15 90 120

0.0

-0.5

-1.0 -1.0

-0.5

0.0

0.5

1.0

1.5

E,V

0

2

4 t,

6

8



(., . 1967)

6.10

+O2 + H2O2 H2O2 O2 +2H+ + 2e­


GOx

+GOx GOx
(red)

(ox)

+ GOx
2

(red)

+ 2Med

(ox)

GOx

e­

(ox)

+ 2Med

(red)

2Med

(red)

2Med(ox) + 2e­

( )