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Estimation of ion-site association constants in ion-selective electrode membranes by modified segmented sandwich membrane method
Maria A. Peshkova, Anton I. Korobeynikov, Konstantin N. Mikhelson Maria A. Peshkova, Anton I. Korobeynikov, Konstantin N. Mikhelson St. Petersburg State University, St. Petersburg, Russia St. Petersburg State University, St. Petersburg, Russia Electrochimica Acta 53 (2008) 58195826 Electrochimica Acta 53 (2008) 58195826

.. ., .. ., .. .. ., ., - -

-

2

· () · · (): (R) (L) · , S ( . .)

K+ -

Ag/AgCl

Ag/AgCl

ClK
+

KCl (3 M)

K

+

-

3

, , , ,, , etc. etc.

« », « » ,

60 (Na+, K+, Cl-, Ca2+, H+, ....) , ,

-

4

,
.. 1979 .

L L L L L L
(«»)

.., . . // 1979. . 15. . 12. . 1822-1824

-

5

:
250

.

... ()
200

150

CL 0 CL=0

100

50

350 300 250

Iz+ + nL

IL

n

K

ILn

C

L

0

... ()

200 150 100 50 0 -50 -7 -6 -5

m

a in +K ina in RT = - (1-2 ) ln iex ijex j ex + ln F ai +Kij aj

) Kilm in in in in RT ai /Ci +aj /Cj m=0 -2 ex ex ex ex k F ai /Ci +aj /Cj ex m (Cl ) Kilm m=0

(C
l

k

in m

*

.., .. // . 1985. . 21. . 540-543
-4 -3 -2

:

E=

RT lgK zF

IL n

+n

RT lgC zF

L

*

lgCL

Mikhelson K.N., Smirnova A.L. // IonSelective Electrodes (E. Pungor edit.) 1988, 5, p. 491-500

-

6

. ?

? ?
: :

K IJ =

k k

J I

K

JR

K

IR

: ( )

kJ K IJ = (K kI

JR

K

IR

)

-

7

:

m

RT (1 - 2 =- F

)

ai in + K ij in a ln ex ex ai + Kij a

in j ex j

1 + Cs /Cr + ln ex 1 + Cs /Cr

in

in ex

ai in /Ci in + a j in /C j in RT ln ex ex -2 ex ex F ai /Ci + a j /C j
-

*

I+ + R

-

IR

K

IR

S+ + R

SR

K

SR

tot S

tot R

S+ ( ):

KIR >>KSR:
:

CIR CR

tot

CIR CR

tot

Mikhelson K.N. // Electroanalysis. 2003. Vol. 15. 1516. P. 1236-1243

CI C
CI C

(

R
IR

tot R

/K

)

1/ 2

C I CS C
CI C
tot R

tot S

/C

(

tot S

K

IR

)

:
E= RT lnC F
tot S

+

1 lnK 2

IR

-

1 lnC 2

tot R

*

Mikhelson K.N., Lewenstam A. // Sensors and Actuators B. 1998. Vol. 48. P. 344-350

-

8

CS 0 CS=0

-

9
1:2 Ca()2
O (CH2)7CH OPO
3

1:1 ClK (Na, NH4, Cs)
O
O O O O

()

NO2

= 24 = 4
Cl

(CH2)7CH

3

O O P O Ca O P O

ClC = 0.01 m = Cl = const
B

_ +

Cl K

R

O O

O

Cl

C

-

= 0.04 m = const

Ca()2

S
: -Cl-
N
+

+

: C 10 90% -

C 10 90% -

-

10
K + NH4 Cs + Na
+ +

... ()

40

30

KIR

K+ + Cl500 400 300 200 100 0 -2.8 -2.6 -2.4

KCl

20

10

K + NH4 Cs + Na
+

+

0

-3.0

-2.8

-2.6

-2.4

lg Ctot +

-2.2

... ()

E=
-2.2

lg C

tot +

-2.0

RT lnCS F

tot

+

1 1 tot lnKIR - lnCR 2 2

-

11
NaCl Cl

35 30

log K log K

KCl

= 3.4 Cl = 3.0 E ()

30 25 20 15 10 5 0 35 30

log K log K

= 3.3 = 3.0

E ()

25 20 15 10 5 0 -3.2
35 30

-3.0

-2.8

-2.6

-2.4

-2.2

-3.2

-3.0

-2.8

-2.6

-2.4

-2.2

log K log K

CsCl Cl

= 3.6 = 3.0 E ()

log K log K

NH4Cl Cl

= 3.5 = 3.0

E ()

25 20 15 10 5 -3.2 -3.0 -2.8 -2.6 -2.4 -2.2 TDDA

25 20 15 10 5 -3.2 -3.0 -2.8 -2.6 -2.4 -2.2

log C

log C

TDDA

-

12 lg K2 = 4.2

Ca()
Ca2+ +
-

2

70 60

Ca()

+ 2

K

1

Ca()+ + -

Ca()

K

2
... ()

50 40 30 20 10

:
E= RT 2lnCS 2F

(

tot

+ lnK2 - lnCR

tot

)

:
C
tot R

-2,4

-2,2
CaCl
2

-2,0

-1,8

0.12

2.1e-2 m 8.4e-3 m 2.2e-3 m

-1,6 -1,4 tot lg C
+

0.06 0.05 0.04 0.03

()

0.08

()

0.1 M 0.01 M 0.001 M
0.12

D+ D- = D
CR
tot

0.04

0.10

()

0.02 0.01

0.08

2.1e-2 m 8.4e-3 m 2.2e-3 m

0.00

0

20

40

60

80

100

120

128 64 RT C = 2 i 2 d d t F

D=

( )

0.00

i -2

-2

(d

d t

)

0

20

40

60

80

100

120

0.06

2

()

(

)

-2

lg D = -7.7 ± 0.5 lg K2 = 4.8 ± 0.7

0.04

0.02 6 7 8 9
1/2

10

()

c

1/2

.., .., ., .. // . 1988. . 24. . 11. . 1487-1490.

-

13

, ?
, , , ,

:
(-)- K+, Na+, NH4+ Cs+ . [4-(1,1,3,3-)] - . , . , , , .
Vladimir V.Egorov, Peter L. Lyaskovski, Irina V. Il'inchik, Valentin A. Nazarov, Determination of Ion Association Constants of Physiologically Active Amines with Cation Exchangers, International Conference on Electrochemical Sensors Matrafured 08, October 5-10 2008, Dobogoko, Hungary, p. 60.

-

14

:
. -, Radiometer, Copenhagen, Denmark Ca- . , University of Memphis, USA Autolab PGstat « », -5557.2006.3