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Дата индексирования: Thu Feb 27 21:13:22 2014
Кодировка:
Поисковые слова: m 103

(wasq@elch.chem.msu.ru)

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

9.8

F
+ ( + G - ) 2 1 WO i = const exp - exp () d RT - 4 RT 1 + exp RT (, , , )

(in situ )

I

peak

= 910U

tun

exp(-9.73( + U tun ))

Au
Utun=const

ln( I

peak

(0.5 - )U tun peak / U tun ) = (6.81 - 9.73 ) - 9.73U
E = E0 + Es=const

tun

I.V.Pobelov, Z.Li, T.Wandlowski, Electrolyte Gating in Redox-Active Tunneling Junctions - An Electrochemical STM Approach, J.Am.Chem.Soc. 130(2008)16045-16054

Au(111) / [Ru(NH3)6]
3+

Au(210) / [Ru(NH3)6]

3+

bare

9

16

L.V. Protsailo, W.R. Fawcett : Electrochimica Acta 45 (2000) 34973505

N.J.Tao, Nature Nanotechnology 1(2006)173

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

· (, ) · · · ..

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

.

(wasq@elch.chem.msu.ru)

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

i =±0.62nFDk2/ 31/ 2v
-3
1/ 2 k

-1/ 6

0 (ck - cks )
0 k

I =±7.34 10 nFD m t (c - c )
2 / 3 1/ 6

s k

I =±6.29 10 nFD m (c - c )
1/ 2 k 2 / 3 1/ 6 0 k

-3

s k

-

, ..

-

111 =+ i id ik

nF (1 - ) nF ( ) 1- - exp - i = i0 exp i0 = nFk s cO cR RT RT RT RT 2.3RT > ln i0 b = = a + b lg i a =- nF nF nF nF ( E - E 0 ) ( ) i = nFk s O exp - RT nF 1 i = nFk s( )cO- cR exp RT (1 - ) gO + g R (n - zO ) F 1 1- i0 = nFk s0 exp exp cO cR RT RT
q F C2 = - 2 = 8 RT 0 c + q c 2 c 2 RT
2

2 =

2 RT q arcsh F 2 2 RT

-
arcsh z ln( z + 1 + z 2 )

0

Fe(OH)2 Fe(OH)3 7.1·10-16 6.3·10-38, . a b Fe3+ Fe2+ 298 , , () 5.0·10-6 /, pH 8. -0.276 (..). 0.5. . -2 0.1 1 -10 /2? ? 0.5, 298 , 78.4.

, , 3 5 1.2 /. 10 , . , 10-5 2/, 1.2·10-3 ·, 1.2·103 /3.

, Bi3+/Bi(Hg), (0.001 Bi) 0.030 -0.015 ( . . .) , 1 M HClO4 1 NaClO4. . 298 . 0.001 /. 0,392 /, 3 . , .
(), () 0,001 Bi3+ (0.001 Bi) (HClO4 +NaClO4), DBi(III) .
(HClO4 + NaClO4), / 1 2 3 4 5 6 7 8
2

, . ... 0.084 0.074 0.081 0.089 0.094 0.102 0.109 0.138

106 DBi(III), c2 -1 5.92 5.00 5.10 5.00 3.97 3.50 3.00 1.60

104 ks, c -1 2.17 1.97 2.25 3.87 24.20 56.70 70.60 60.60

0.965 0.927 0.885 0.832 0.774 0.704 0.628 0.543

0.29 0.28 0.24 0.33 0.54 0.67 0.82 0.72