Äîêóìåíò âçÿò èç êýøà ïîèñêîâîé ìàøèíû. Àäðåñ îðèãèíàëüíîãî äîêóìåíòà : http://depni.sinp.msu.ru/~piskarev/Articles/ChEn_2011_6.pdf Äàòà èçìåíåíèÿ: Mon Nov 7 22:22:48 2011 Äàòà èíäåêñèðîâàíèÿ: Thu Feb 27 20:18:48 2014 Êîäèðîâêà:

, 2011, 45, 6, . 543­547


535.426


© 2011 . . . *, . . **, . . **, . . **, . . ***
* () 620031, ., , . , 59 ** 603005, , . , 10/1 *** .. .. 119992, , , 1 E mail: i.m.piskarev@gmail.com
09.03.2011 . 11.04.2011 .

Fe2+ 2. ( 6) ( 12) . , . , . .

(, ) . ­ . , (, , ..). , , [1­3]. , · , . , , . , , [4, 5]. , , [6, 7]. , ,

( 30 ). , [2]. 6.8­7.8. , . , . , , , , . , , . , , , .

543


544

.

06 (. ). . 1 : 0.4 2, 0.4 FeSO4, 0.2 22 1.1 ( 0.1 ). , . ( 2), ( 6) ( 12) . , FeSO4 ­ , 2, 6 12, . 150 (. ) 2 2SO4, 12 ­ NaOH. , ( 6). 10­15 . 0.5­1.0 c FeSO4. . , . , , . . 02 ( ). , = 304 , = 2200 ­1 ­1). MathCad 11. . (1)­(17) (). OH­ H+ ( ) . OH·, HO i2, Oi2-, ; - H2O2 HO 2 + H+, pKa = = 11.5 ( (12), (13)) HO i2 H+ + + Oi2-, pKa = 4.8 ( (7), (8)). [8].

Fe3+ + 3OH­ Fe(OH)3 ( (18), (19)). . Fe2+. N(Fe2+ Fe3+) ( 2) [Fe2+] > [H2O2] [H2O2] = 10­6 / . Fe2+, , Fe2+, ( (11)) Fe3+. Fe2+ 10­2 10­5 / N(Fe2+ Fe3+) 2 â 10­6 /, .. 2 â â [H2O2]. , . , . [Fe2+] < [H2O2] 2 . ( (11)), , Fe3+. , N(Fe2+ Fe3+) [Fe2+], . , , .. "" , (11). = 304 , . [Fe2+] > [H2O2] ( [Fe2+] 100 ) 6, 60, 600 6000 [Fe2+] = 10­2, 10­3, 10­4 10­5 / . ( 2) , , · ( (1) (4). , [Fe2+] = 10­3 [H2O2] = 10­4 /, 2 60 , . 1. , , , Fe3+, Oi2- . , Fe3+ , Oi2- . ( 6)
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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 Fe2+ + H2O2 Fe3+ + OH· + OH­ OH· + H2O2 HO 2 + H2O
i

545

, /( ), [8] k1 = 56 k2 = 3 â 107 k3 = 8.3 â 105 k4 = 3 â 108 k5 = 5.5 â 109 k6 = 7.1 â 109 k7 = 7.5 â 106 k8 = 1.2 â 102 pKa = 4.8

HO 2 + HO 2 H2O2 + O2
Fe2+ + OH· Fe3+ + OH­ OH· + OH· H2O + 1/22 OH· + HO 2 H2O + O2
i

i

i

HO 2 H+ + O
i-
i i i-

i

i- 2

H+ + O 2 HO

i 2
-

HO 2 + O 2 HO 2 + O2 HO 2 + OH­ O 2 + H2O
i-

k9 = 9.7 â 107 k10 = 1010 k11 = 1.9 â 109 k12 = 2 â 10 2 k13 = 1010; pKa = 11.5

O 2 + Fe3+ Fe2+ + O2
H2O2 HO 2 + H+
-

i-

HO 2 + H+ H2O2
OH· + HO 2 HO 2 + OH­ Lum + OH· LOOH· LOOH· + O 2 P*
i-

-

-

i

k14 = 7.5 â 109 k15 = 8.7 â 109 [9] k16 = 1 k17 = 1010 k18 = 1 (pH 6) k19 = 106 (pH 12)

O 2 + OH· + H+ H2O + O2(s)
Fe3+ + 3OH­ Fe(OH)3 Fe3+ + 3OH­ Fe(OH)3

i-

( (18)). 600 , , . ( 12) ( (19)), ( 30 ) . . . , , [2, 3, 9]. ( (15)), LOOH·. LOOH· , . ,
5
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LOOH·. , LOOH·, ­ LOOH·. [Fe2+] > [H2O2], 2. . LOOH· 1000 [Fe2+] = 10­3, 10­4 10­5 /, [Lum] = 10­4 / . 2. , , [Fe2+] = =10­3 / 60 . [Fe2+]= 10­4 / 600 , 10 , 10 , .. /


546 lg , / ­7 ­8 ­9 ­10 ­11 ­12 ­13 ­14 ­15 ­16 ­17 0 10

. lg P*, /( ) ­14 ­15 1 ­16 2 3 ­18 0 4 20 30 40 50 t,
. 3. P*, /( ), . . 2 (1) 12 (2).

2

­17 1 2 4 6 8 10 t,

. 1. lg c (/) [Fe2+] = 10­3 / [H2O2] = 10­4 /, 2 t (). 1 ­ OH· ; 2 ­ O 2 ; 3 ­ HO 2 ; 4 ­ HO
i- - i 2.

. 6000 [Fe2+] = 10­5 / , / . LOOH· Oi2- ( (16)). *. *, [9], 1 .
lg dc, /( ) ­7 1 ­8 2 ­9 3

, . , * , (16) 1. * : d [P *] dt = k16 LOOH i][O i2- . *, [Fe2+]= 10­3 /, [H2O2] = 10­4 / [Lum] = =10­4 / 2, 12 , . 3 ( 1). O i2- (. 1). . 3 ( 1) , 0.7 * , 1000 . , . * 0.7 5.15 â 10­15 /, 12 ­ 5.39 â 10­15 /. , , 0.5­1.0 , . , . 2 , . 4. . , , , , 06 0.5­1.0 . , , , , . 2
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­10 0 200 400 600 800 t,

. 2. LOOH· d, ­1 ­1 , t ­ , . 1 ­ [Fe2+] = 10­3 /, 2 ­ [Fe2+] = 10­4 /, 3 ­ [Fe2+] = 10­5 /. [H2O2] = 10­5 /, 10­4 /, 2.


S, .. 0.7 0.6 0.5 0.4 0.3 0.2 1 0.1 0 5 10 2 15 20 25 t,

547

[10]. [Fe2+] , . , Fe2+ Fe3+, Fe3+ . . 1. ( 100 ) [Fe2+] > [H2O2] 6, 60, 600 6000 [Fe2+] = 10­2, 10­3, 10­4 10­5 / . 2. , 5 , . 3. , , .
1. . / . .. .: . . ., 1961. . 138. 2. .. // . . . 1966. . 89. 3. . 409. 3. .., .. // . . . 2009. . 49. . 341. 4. .., .. // . . . 2007. . 79. 4. . 34. 5. .. .., .. // . . . .. . . , . 2009. . 22 (61). 3. . 35. 6. .. // . . 2006. 2. . 183. 7. .., .., .. // . , 1983. . 179. 8. .., .. . . .: , 1982. . 201. 9. .., .. . .: , 1989. 10. .. // . . . 2007. . 11. 1. . 3. 5*

. 4. (S, . .), t ­ , . [Fe2+] = 10­3 , [H2O2] = 10­4 , [Lum] = =10 4 /. 1 ­ ; 2 ­ .

(. 4, 1) (2). 30 ­ 1.7 106 (2.3 â â 10­15 /), ­ 4.1 106 (5.6 â 10­15 /). 2.5 . [LOOH·] 10­5 /. 10­10. . 12 (. 3, 2), ( (19)). , ( (11)) , O i2- , [*] . 12, [Fe2+] = 10­3 / [H2O2] = 10­4 / 105 2. , . . , , .
45 6 2011