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ISSN 1810-0198. , .18, .

5, 2013

620.193.013




..
: ; ; ; ; .
( ) () , .
, . , , .
, ,
.




, , ,
.
.
() - [1
2]. ()

( ).

( = 1,00 ; = 10 .) [1]. , .

(. . .).
()
(u) [1]
(Fe) [3].

-2 (7)
-7 (500).
, , () JEOL-6380LV.
() INCA Energy-250 [3].


Cu (99,9 %) Fe (0,005 % ). (1102 NaOH
( = 11) u) 0,2 M H3BO3 + 0,05 M Na2B4O7
(pH = 8,5) Fe) NaCl ( = 1,0104 1,0101 )
(Gly) ( = 1,0106 1,7101 ) 20 .

IPC-Compact (
(Vp). 830 ( 0,1 ). ()
Cu Fe
2160



-
. [1] , 1102 NaOH
= 11
. - , (l) = 1104 , (),
(. 1),
() (. 1) Cu
(. 1), -
() .

ISSN 1810-0198. , .18, .5, 2013

. 1. () 1102 Na + 1102 NaCl () (1/1-Cu/Cu2O, 2/1,2-Cu2O/CuO,


Cu(OH)2, 3/3-Cu/uCl); () , () ( )
((-7) 500)

1

( )
= 0,15 1102 Na + 1102
NaCl,
( )

47

Cl

Cu

47

, (Cl) = (1103 1102)


, /,

(. 1).
,
Cl , ,

.
[4] [56]. , ,
CuCl
Cu - = 8,4
[7] .
,
Cl-.
- .

(Gly),
Gly [8].

Gly. [1] , = (1106 1105 )


, . Gly (1104 1103)
. ,
1 (
Cu2),
,
3 ( = (0,120,03) ) (. 2), , Cu Cu (II) c Gly. [9].
Gly CuOH+ [10],
- , .
= 5103, , ,
= (5103 1102 ) . , (. 2), Cu, ,
(h > 3 )
d = 23 .

[11], ,
,
.

Gly ,
= 1102 , (. 2).
Gly > 1102 .
Cu (
= 1,00 +1,00 ):
, [12].
2161

ISSN 1810-0198. , .18, .5, 2013

. 2. 1102 NaOH + M Gly, = 0 (1), 1104 (2), 1103 (3), 5103 (4), 2102 (5)

2

1102 NaOH + 5103 M Gly,

( )

Cu

93

, ,
/,
= 5103
(. 2), [13].
.

Gly -.
[9] ,
[14], nGly = 0.


Gly [1] , -
( OH Gly-) 2162

.
, ,
, = 0,100,12
, -
, ,
. Gly
= (5103 1102)
( = 0,500,70 ),
Cu CuO [9].

- . Cl- ( = 8,4). NaCl ,
. 5104 NaCl,

NaCl = 5104 5,0103 ,
, Fe .
NaCl = 5104 1,5103 .
, ,
NaCl
, ,
(. 3). Fe,

-, : 1) (
1); 2) 1 2 (
- , );

ISSN 1810-0198. , .18, .5, 2013

3) 4) [1518]. [19
20], -
( = 0,540 (+0,224) ),

.
M/ (. 4),

.

. 3. 0,2 H3BO3 +
+ 0,05 Na2B4O7 + 1103 NaCl ( = 8,4), : 1 2; 2 3; 3 10;
4 20; 5 30; 6 40; 7 50 /



(Vp)
(. 3) Cl-,
[2122].
1 2
(0,388 +0,210 , ), ,
1.
[23]
.
,

Fe3+
.
lgimax (1) = f[lgVp]
lgimax (2) = f[lgVp] 0,50,6 , -
Fe
[21],
- .
NaCl
, , Nacl = 1,5103 M
Fe .
, u, [2, 24,
25], Fe . Cl ,
, . Cl-
OH-, . Cl-
. , Fe - [26]:
Fe()2 + Cl [FeClOH]ads + H+ + e;
[FeClOH]ads = FeClOHads + e;
FeClOHads = Fe2+aq + Claq + OHaq .

)
. 4.
0,2 H 3BO3 + 0,05 Na2B4O7
( = 8,4) Vp = 2 / () 50 / (),
1,500

(1)
(2)
(3)


/,
Fe l. , Cl-, , , .
nCl 1 [27], (1), . . Fe
NaCl .

Vp. Fe
(. 5, . 3). , ,
,
Vp = 50 /c.
2163

ISSN 1810-0198. , .18, .5, 2013

3

0,2 H3BO3 + 0,05 Na2B4O7 +
+ 1103 NaCl ( = 8,4)

Vp,
/

2
10
30
50





81
64
43
20

3
4
5
8

:
-7 500.

)
. 5. 0,2
H3BO3 + 0,05 Na2B4O7 + 1,5103 NaCl: ) Vp = 3 /;
) Vp = 50 /

, ,

NaCl ,
NaCl (C = 5,0104 1,5103) ,
-, .


- . , ,
Gly-.
,
CGly = (3,0102 5,0102) . , (4102 5,0102 ) Fe


.
,
, Gly = (3,0102 3,8102)
(. 6).

(. 6), .
Gly 1. Fe [28],
, .

. 6. ) 0,2 H3BO3 + 0,05 M Na2B4O7 + X M Gly (1 X = 3,0102; 2 X = 3,4102; 3 X = 3,6102;


4 X = 3,8102) (Vp = 3 B/c) ) (1) (500).

2164

ISSN 1810-0198. , .18, .5, 2013


/ ,
,
(. 7). /
0,2 H3BO3 +
+ 0,05 Na2B4O7 + 3,0102 Gly N ,
,
[Fe(OH)n1Glyk]z2 [28].
Gly
. (, ),
, (

[23]. Gly, ,
1 2, (0,060
(0,140)) .
0,2 H3BO3 + 0,05 Na2B4O7 +
+ 3,0102 Gly ( = 8,4)
Gly,

[2930].
:

lgimax = flg(Vp) , , ,
(dlgi)/(dlgVp) 0,60,7 [2122]

1
2,
(Fe3+) [23],
- .
Fe , Vp
( 3 ), Vp = 3050 /c
. ,
, Vp Fe
,
/ , N .
,
( = 8,4) Gly-
, Gly

[Fe()n]sz1n + k Gly = [Fe()nk Glyk]z2 +


+ k + (z1 z2)e ;
[Fe(OH)n]z1n [Fe(OH)n1]z1n+1 + ;
[Fe(OH)n1]z1n+1 + k Gly = [Fe(OH)n1Glyk]z2,

, (. 7),
.


N [3].


[27]. nGly 0,05,

[Fe(OH)n]z1n [28].
,
, Gly .
, , Gly c

,
1 2 (. 8),
. ,
, , , 1, . -

)
. 7.

0,2 H3BO3 + 0,05 Na2B4O7 + 3,0102 M Gly
(Vp = 3 / ; Vp = 50 / )

2165

ISSN 1810-0198. , .18, .5, 2013

5
4
3
2
1

. 8. 0,2 H3BO3 + 0,05 Na2B4O7 + 0,03 Gly, :


Vp = 1 3, 2 10, 3 20, 4 30, 5 50 /c

C = 3,0102 ,
.
,
Fe .

-


.

- , ,
.
, .

, ,

.

.., .., .. // :
, . 2004. 5. . 5.
2. .., .., .., .. //
. 1999. . 35. 1. . 27.
3. Borisenkova T.A., Kaluzhina S.A. // ECS Transaction. 2009. V. 6.
43. P. 179.
4. .., .., .. //
. 2004. . 6. 1. . 58.
5. Okada . // J. Electrochem. Soc. 1984. V. 131. 2. P. 241.
6. Okada T. // J. Electroanal. Chem. 1991. V. 297. 2. P. 349.
7. .., .. // . 2001. . 37.
3. . 266.
8. : 7 . .:
, , , 2002. 1271 .
9. Skrypnikova E.A., Kaluzhina S.A., Popova E.V. // ECS Transaction.
2008. V. 13. 27. P. 7.
10. .. . .: - , 1959. 206 .
11. .., .. // . 1989. . 25. 7.
. 952.
12. .. // :
. 1985. . 4. . 3.
1.

2166

13. .., .., .. // : , . 2007. 2. . 41.


14. .., .. // : , .
2008. 4. . 41.
15. .., .. //
. 2008. . 10. 3. . 223.
16. Szklarska-Smialowska Z., Viefhaus H., Janik-Czachor M. // Corros.
Sci. 1976. V. 16. 7. P. 649.
17. Sato N. // Electrochim. Acta. 1971. V. 16. 10. P. 1683.
18. Janik-Czachor M., Szummer A., Szklarska-Smialowska Z. // Corros.
Sci. 1975. V. 15. 12. . 775.
19. .., .. // . 1987. . 23. 3.
. 303.
20. Aramaki K., Mizoduchi M., Nishihora H. // J. Electrochem. Soc. 1991.
V. 138. 4. . 394.
21. ..
. : , 1989. 464 .
22. . / . . .: , 1985. 496 .
23. .., ..
. 2004. 3. . 38.
24. .., .. // . 1982. . 18. 2.
. 198.
25. Strehblow H., Titze B., Loechel B.P. // Corros. Sci. 1979. V. 19. 12.
. 1047.
26. Foley R.T. // Corrosion. 1970. V. 26. 2. P. 58.
27. .., .. // . 1984. . 20. 3.
. 424.
28. .. .
.: - , 2008. 240 .
29. .. // . . . .. . 2000. . 1.
. 161.
30. .., .., .. // .
1985. . 21. 12. . 1690.

:
, 08-03-00194.
15 2013 .

Kaluzhina S.A. MODERN APPROACHES TO ANALYSIS


OF LOCAL DEPASSIVATION KINETICS OF COPPER AND
IRON UNDER INORGANIC AND ORGANIC ACTIVATORS
The effect of inorganic (sodium chloride) and organic (glycine) substances at anodic behavior of copper and iron in alkaline
mediums, where depassivation of metals is possible, is investigated. Series of electrochemical and physical methods, determining common and specific regularity of pitting process, was used
for systems analysis. Their dominating factors taking account of
metal nature, electrolyte composition, phenomena of competitive
adsorption and complexion are established. On the basis of modern
theories, confirmed by experimentally, the supposition about pitting process mechanism in studied systems is stated.
Key words: copper; iron; pitting process; mechanism; sodium
chloride; glycine.