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Поисковые слова: m 31

.

(wasq@elch.chem.msu.ru)

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

10
7 6 5

4 3 2 1 0 0 2 4 6 8 10

-- 4.9 10.0

2 zi2 e0 1. -Gs = N A 8 0 ri

1 1 -
0

2. =

1l = sR

z = 2 (4.6.14) (4.6.15) = + ( ) z + | z- | b = + b[11] = 2b[1 0 0 = - (2b + bp ) c 2 [c] = [/] b =| z+ z- | b[11] = 4b[11] [c] = [/ 3 ][/ 3 ] = = z+ + c z- - c z = 2; = 1
0 + 0 -

1 = 100 1 100 - 22.1 1- 1-

1]

3. G

= H TS

G1 = nFE0

G2 = G1 G

G

Cu

G
2

1

Cu2+

CuAu9

G

G E0 = E0 - nF G 2.3RT 2.3RT E = E0 + lg fc = E0 - + lg fc nF nF nF

E = E -

4. E = E0 +

aZn2+ aEDTA4- f 2cZn2+ f 4cEDT 2.3RT lg aZn2+ = K= nF aZnEDTA2- f 2cZnEDTA2- Zn2+/Zn
2.3RT lg a nF
Zn
2+

A4

-

z =2 f z =4 f

2 4

z 2h J lg f =- 1+ J

E =

( ) ( )

(electron transfer)

: .., - . ., , 1959.

1 : = v

8.1-8.2

k

1 vk

= =

:

ck (t , x, y, z )

j

() k

=j

() k

+j

( ) k
)

+j

( ) k

ck =- div jk( t

i =± nFj

() k

i( E )

I

8.2

j =- Dk grad ck
II

c i =± nFDk k x d 2ck =0 dx 2

x =0

ck 2ck = Dk 2 0= t x

0 dck ck - cks = const = dx k

0 s cO - cO i = nFDO O 0 cR - c i =- nFDR R 0 s R 0 cO = nFDO O ( idO ) - c= bO ( id R ) - s cR = bR s O

i i

(O ) d

(R) d

c =- nFDR

0 R R

nFDO O i nFDR ; bR = R ; bO =

i

s RT cO E=E + ln s nF cR ( ( RT DR O RT idO ) - i RT idO ) - i E=E + + = E1/ 2 + ln ln ( ln ( nF DO R nF id R ) + i nF id R ) + i 0 ( ( idO ) - id R ) P ( E ) i= 1 + P( E )

nF P ( E ) = exp ( E - E1/ RT

2

)

8.4

i =±0.62nFDk2/ 31/ 2v

-1/ 6

0 (ck - cks )

(1943) · · n · D · ( ) · ( )

.., .. (1959) · (, ..)

Chanel microband (« »)
· (injection technology)

. (1922)
ck 2ck = Dk 2 t x
0 ck - cks i =± nFDk Dk t 0 0 ck ( x, 0) = ck ck (, t ) = ck

8.5

ck (0, t ) = cks = const ( E = const )

(1934)
1 0 I =±7.34 10-3 nFDk / 2 m 2 / 3t1/ 6 (ck - cks ) 1 0 I = ±6.29 10-3 nFDk / 2 m 2 / 31/ 6 (ck - cks )

E = E1/ 2 +

RT I d - I RT D ln ; E1/ 2 = E 0 + ln R 2nF DO nF I

I=

Id 1 + P( E )

8.5

I

d

.

(Electrochemical Impedance Spectroscopy, EIS) E = Ecp + V sin(t )

8.6, 9.4

: (., 1899) W W RT 1 1 ZW = ; W= 2 2 -j +0 0 c D n F 2 O cR DR O RT : = i0 nF 1 W W (Nyquist diagram) = Rs = + Cs

. ... .., . ., , 1973.

E = E ± vt

8.6

~ 1 t

c 0 - c s (t ) i = nFD (t ) nF 0 i = nF DO v cO f ( ); RT (., . F 3 3/ 2 1/ 2 1/ i = 0.4463 n DO cO v RT
1/ 2

nF nF vt ( E - E ) = RT RT , 1948) =

2

E = E1/ 2 - 1.109

RT nF

E - E = 2.3 i (i )0 = + i i

RT nF 0.485(i ) i

0

+ 0.086

(.)

(E v) (E v)

9.4

(E v)

RT E = E - F
0

1/ 2 1/ DO 2 Fv 0.780 + ln + ln ks RT

i = const

8.7

E = const

s 0 cO = cO -

2i nF

t DO

s cR =

2i nF

t DR

s s cO = const ; cR = const 0 ck - cks i =± nFDk Dk t

RT - t ln nF t ( ) E = E1/ 2 +

( )

8.7

i = 4nFDcr

(SECM)

· (, , ) · · ·

Mirkin, B.R.Horrocks, Electroanalytical measurements using the scanning electrochemical microscope, Analytica Chimica Acta 406(2000)119-146

«»
TCNQ2 [Fe(CN)6]
4-

TCNQ

·

TCNQ

[Fe(CN)6]

3-

t
40 s

1s

C. Amatore et al. / Electrochemistry Communications 2 (2000) 353358

E. Ahlberg et al. / Journal of Electroanalytical Chemistry 548 (2003) 85/94 S. Valizadeh et al. / Electrochimica Acta 47 (2001) 865874