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. . I II .
- - « » ( ) - - «» 1 -


6.1 ­ 6.4

/
. , 1929:



d G =- SdT + Vdp +
-
= - =


i


i dN i + F


i

zi dN

i = i + zi F
i

= +
-



-
zF

, 1889
z+

RT = onst + ln a zF


M

z

M

+ ze = M ; E = E o +

RT ln a zF

M

z

I

M + A - + ne =+M +- Az-; E = Eo -

RT lnaAz- | z- | F

II
2


7.10




«»



M2 M1

1 = (WeM1 - WeM e0

M1||M2|M1
2

)

E =
M p

M2 M1

+

M p

1

-

M p

2

.., ~1950

EK =

() = ­ 4.44

W + e0

M e


3


6.5 ­ 6.8




M M
+

M



+ M +e



= onst -

RT ln ae F

+ e

M

+

0 = ­2.87 ()


F.Donnan, 1911 - (1) (2),

+

--

ED =

(1)

-

( 2)

(1) ( RT a- RT a+2 ) = ln (2 ) = ln (1) F a- F a+
4


6.4



I

M

z+

+ ze = M ; E = E o +

RT ln a zF

M

z

M + A - + ne =+M +- Az-; E = Eo -

RT lnaAz- | z- | F

II

- : ­ , (, - ). : , (, ).

5



Reference electrode Potential versus SHE, V (aqueous systems, recommended values for 25oC) Mercurous bromide, 0.241(2) 0.280(1) 0.333(7) 0.197(6) Silver cyanide, oxide, bromate, iodate, perchlorate; nitrate 0.6151(5) 0.098 chloranil, 1,4naphtoquinhydrone 0.586(8) 0.641(4) Ag/Ag2SO4, Pb/Pb2SO
4

Analogues

Media

C

alomel electrodes saturated (SCE) normal (NCE) decinormal

aqueous alcohols or dioxane) aqueous, mixed, abs. alcoholic aprotic aqueous, mixed aqueous, mixed any with sufficient solubility of components
6

iodide, iodate, acetate, and mixed (with oxalate electrodes

Silver-chloride electrode (saturated KCl)


Mercury-mercurous sulphate electrode Mercury-mercuric oxide electrode Quinhydrone electrode 0.01 M HCl 0.1 M HCl





M.Pourbaix, Atlas d'Equilibres Electrochemiques, Gauthier-Villars, Paris, 1963 R.Parsons, Redox Potentials in Aqueous Solutions: a Selective and Critical Source Book, Marcel Dekker, New York, 1985; A.J.Bard, R.Parsons, J.Jordan, Standard Potentials in Aqueous Solution, Marcel Dekker, New York, 1985. CRC Handbook of Physics "HSC Chemistry" database
7


All-solid-state reference electrode

: - Quasi reference electrode - Dynamic reference electrode
8


4.1 ­ 4.4, 6.2


.Planck, 1890
II





RT =- F


I i

ti d ln ai zi

P.Henderson 1907-1908 - -

zi j+ j- = ; ji = - Di gradci - ui ci grad ; Di c+ c- | zi |

1-

RT ui | zi | F
-

ui ti = ui
i





D- - D+ cII RT RT t- t+ cII ln =- + ln F z+ D+ + | z- | D- cI F z - z + cI

9


M.Pourbaix (. )



, : -6 1 -2 10

10


Tl2O3+


Tl2O3-

!



11




- Pb2+/Pb PbSO4/Pb, SO42- 298 ­0.126 ­0.355 c. PbSO4.

. - u+/u [u(CNS)2]-/Au 298 1.70 0.69 c. [u(CNS)2]-.
, LiCl (1 M)/( Li,Hg) 298 -2.20 . ... -2.044 . LiCl 0.774.

12