. , , (). , 2 2. , .
. , . , , , . , , , . , , , , , .
[1,2], , . , , . , , , - [2]. ( , , , 10-2÷10-5 /∙ [1]), , .
, , . , - .
, . .
|
|
, - , [3].
. ( =30÷40 -1), (.1).
) | ) |
.1.) : 1 - ; 2 ; 3 ; 4 ; 5 . ) . |
: 300 [4], [5] , .2. (IV), (II) (II).
. .3.
( 1), .
1 10 ;
2 50 .
.2.
[6], () . (II),
(IV) (II) (.3). , , , .
.3. (), ( 4). ( 2) ( 3). [3]. . , , - .
VOSO4<Mn2P2O7 <MnSO4 :
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|
1. MnSO4 , -, ( 5 k=1,2∙104÷4∙103 [6] /∙) , -, - , .. MnIII/MnII, MnIV/MnII MnVII/MnII 1,51 ,
=298 ; V=400 ; [3]=1,5∙10-3 /; [2]=1∙10-3 /; [22]=1∙10-3 /; [VOSO4]=[Mn2P2O7 ]=[ MnSO4]=0,044 /.
.3.
1, VOSO4 - 2,
Mn2P2O7 - 3, MnSO4 - 4.
1,58 1,51 [7,8], .. , , .
2. : , [9], 9∙103 /∙. MnIII, , , (MnIII3-3MnIII) [(2)4MnIII3--3MnIII(2)4]2+. - MnIII , , , .
3. (k=13,3 /∙ [6]), - , 0,044 [8].
, . , .
.. .
:
1. .., .., .. : . : , 2000.- 318. ISBN 866-590-241-5
2. .., .., .. : . : . ., 2004.- 272. ISBN 966-590-458-2
3. .. : - . : 05.17.05. ., 1982. 330. .
4. .., .., .., .. // . 1990. .12, 5, .459-461.
5. .. . .: , 1984. - 448.
6. .., .. г : . : . ., 2007.- 415. ISBN 978-966-590-751-0
7. .. . .: , 1971. -467.
8. .. - . .: , 1989. 248 . ISBN 7245-0343-3
9. .. : - . : 05.17.05. ., 1987. 330. .
541.127: 542.943
.., .., ..,
έȭ
: . . , . , - . .1, . 1, . 10.
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[1] , . , , . (9,5%) (3,5 %) .
.
278 (II) , , , (.1). . 2 , 11,0-12,0%.
. (5-9 .) (II) (III), (.1). . , , . (.1).
(275-278). 110,0-114,0 % . : -, (3і+=) [2].
1
(II) 278. [ArCH3]o= 0,4; [Mn(Oc)2]o= 0,18; [2SO4]o= 1,2; [O3]o= =4,010-4 ∙ -1; V. = 0,01 ; τ = 0,83 . ( - τ = 1,3 .).
, ∙ -1 | , % | ||
- | -- | ||
2- | 0,221 | 0,040 | 65,3 |
3- | 0,251 | 0,054 | 76,3 |
4- | 0,253 | 0,056 | 77,2 |
1 ; 2 ; 3 ; 4 ; 5 (III)
[ArCH3]o= 0,4; [Mn(Oc)2]o= 0,18; [2SO4]o= 1,2; [O3]o= 4,010-4 ∙ -1; V. = 0,01 ; τ = 1 .; .
.
.1 4- (II) 278
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[3-5] :
ArCH3 + O3 → Ar H2 + HO + O2, | (1) |
ArCH3 + O3 → ArCH2OH + O2, | (2) |
ArCH3 + O3 → , | (3) |
Mn2+ + O3 + H+ Mn3+ + HO + 2, | (4) |
ArCH3 + Mn3+ Ar H2 + Mn2+ + +, | (5) |
Ar H2 + O2 ArCH2O2, | (6) |
ArCH2O2 + ArCH3 → ArCH22 + r 2, | (7) |
ArCH2O2 + Mn2+ + + → ArCH22 + Mn3+, | (8) |
ArCH2O2 + 3 → ArCH2O + 22, | (9) |
ArCH22 → ArCH2 + , | (10) |
ArCH22 + Mn2+ → ArCH2¯ + Mn3+ + HO, | (11) |
2ArCH2O2 2ArCH2O + O2, | (12) |
ArCH2O + Mn2+ ArCH2¯ + Mn3+, | (13) |
ArCH2O¯ + =+-3 ArCH23, | (14) |
2 ArCH2O2 ArCH2 + ArCH + 2, | (15) |
ArCH2 + =+-3 ArCH23 + +, | (16) |
ArCH + (3)2 ArCH(3)2 | (17) |
278288 (.3), 20% . , -, (.123615), (1), (2) (3) [3-6]. , (2), (14) (15), (15) (17).
, , (4) n(III) ( [r3]0 = 0,4; [n()2]0 = 0,18; [3]0 = 4,010-4 -1, 1-3 = 0,59; 4= 19,2 -1-1; W4= 1,410-3; W1 - 3 = 9,510-5 -1-1, .. W4:W1-3 = 15:1), (5) (W5=10,010-30,40,18=7,210-4 -1-1). (6) , (7,8,9) ( ) (12) (15).
, =278; [r3]=0,4; [n()2]=0,18; [ArCH2O]=10-6 -1 7=0,23 [7]; 8= 10,0 [7]; 9 =103 [9]; 15 = 108 [7] -1-1, W7 = 910-8; W8 = 1,710-6; W9 = 410-7; W12 ≈ W15 ≈1,610-4 -1 ( ). , (7), (8) (9) , (5) (12) (15), .. , -, - . ν = W8 W12-1<<1. : (II); ; n(III) n(II).
(6) , (12), (15) [7]. (12)(13)(14) (.12) . [10], , [9], (II) (.13), - (.14), .
(15) , (15) . , .
, (II) : (4) (5) (6) (12) (13) (14). , , :
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r3 + n2+ + 3 → r2¯ + n3+ + +1/22 (26)
, :
r = [r3]0[n()2]0[3] (27)
, , :
ArCH2O3 +n2+ Ar HO3 + n3+ + +, (28)
Ar HO3 + 2 Ar O3, (29)
2Ar O3 2 Ar O3 + 2, (30)
Ar O3 + n2+ Ar O3 + n3+, (31)
Ar O3 + =+-3 ArCH(O3)2 (32)
, , 4-, :
(33)
4-; 278 (=0,205; 1+2+3=0,59; K5 =10,0∙10-3-1-1; [ArCH3]o=0,4; [Mn(OAc)2]o=0,18; [O3]o=410-4 ∙-1). 89,4 %, (77,2%).
. , , , , , .
- , (55,363,3%) , (10,014,0%).
:
1. .. - / .. , .. // . 2006. .79, 1. . 125 128.
2. .. / .. , .. , .. // . 1994. .35, 2. . 255260.
3. .. / .. .: , 1990. 751 .
4. .. / .., .., .. : , 2004. 272 .
5. Galstyan G.A. The kinetics and reaction mechanism with alkilbenzoles in liquid phase / G.A. Galstyan, E.V. Potapenko, I.M. Pluzhnik, A.G. Romanenko, A.G. Galstyan // Regional Conference on Ozone Generation and Application to Water and Waster Treatment. Moscow. 1998. P. 667 694.
6. .. / .. , .. , .. // . 1992. T.35, 4. C. 779 877.
7. .. / .., .., .. : , 1975. 336 .
8. .. - / .. , .. // . 1978. .18, 4. . 615 621.
9. .. / .., .., .. .: , 1965. 375 .
10. .. / .. .: , 1971. 711 .
547.657+547.541.112
.., .., ..