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139

, 2012, . 54, N 2, c. 139142


. . , . . , . . , . . *,
. . , . .

- ,
. . . . ,
123060, , . , 5; * e-mail: march@bochvar.ru

25.04.2011; 05.10.2011

546.175-323:547.497.1

. ,
[HNO3] = 37 / d[(NH2NH)2CO]/dt =
k[(NH2NH)2CO][HNO3]n, n = 3.6 2.9 70 90C . k = (6.65 0.23)
104 2.9/(2.9) 90C, 7 / HNO3
124 /. Fe(III) Tc(VII) , . , NO2+.
: , , , , , , , , , .

[1] Pu(IV) Np(VI) (NH2


NH)2CO. Pu Np
. , , HNO3.

,
.
.

.
H2O HNO3,
,
(NH2NH)2CO.
.
0.1 / HNO3
97% Acros Organics (). U(VI)
UO2(NO3)2
6H2O .. .

. Tc(VII) NH4TcO4
98%. Fe(III) Cr(III)
... 1 / HNO3. U, Tc,

Fe Cr - . HNO3
..

0.1 / NaOH.
(NH2NH)2CO
[2], -
(). . (NH2NH)2CO 25 ,
0.5 5%-
2.5 / H2SO4,
, 15
420 . . 1.
(VII) 100 /
, UO22+ .

UO22+ (NH2NH)2CO

. 1. -.

140

. . .

(NH2NH)2CO UO22+.
-, (NH2NH)2CO 20% 10 / U(VI).

,
(20 2)
8 /, (7090).
(NH2NH)2CO
.
lg[(NH2NH)2CO] (. 2),
. , ( )
d[(NH2NH)2CO]/dt = k[(NH2NH)2CO].

. 2. lg[(NH2NH)2CO] 90,
[(NH2NH)2CO] = 0.1 / [HNO3], /: 1 3, 2 5, 3 6,
4 7.

. 3. lnk ln[HNO3] 70 (1) 90 (2).

(1)

, ,
. 1.
. 1 , HNO3 (NH2NH)2CO . HNO3,
lnk1ln[HNO3]
(. 3), 3.6 2.9 70 90 .
,
(NH2NH)2CO HNO3

. 4. k [HNO3] = 7 /
[(NH2NH)2CO] = 0.1 /.

d[(NH2NH)2CO]/dt = k2[(NH2NH)2CO][HNO3]2.9 (3)

Tc, Fe Cr 7 / HNO3
0.001 /, [(NH2NH)2CO] =
0.1 / 90. , . 5 . 2, ,

90.
k1 = 1.34
0.06 3.6/(3.6) k2 = 6.65 0.23 2.9/(2.9).

1. k HNO3 [(NH2NH)2CO] =
0.1 /

d[(NH2NH)2CO]/dt = k1[(NH2NH)2CO][HNO3]3.6 (2)

70


7095 7 / HNO3. (. 4),
E = 124 16 /.
,
Fe Cr -
,
, , U
Tc, (NH2NH)2CO.

[HNO3],
,
/
3
70
5
70
6
70
7
70
3
90
5
90
6
90
7
90

k, 1
0.0007
0.0042
0.0091
0.0143
0.016
0.072
0.125
0.178

k1105,
/(3.6)
1.34
1.28
1.44
1.30

1.34 0.06
3.6

k1 = k/[HNO3]3.6; k2 = k/[HNO3]2.9.

k2104,
/(2.9)

6.61
6.76
6.92
6.30
6.65 0.23
2.9

141

. 5. (NH2NH)2CO 7 / HNO3
90 0.001 / Cr(III) (1), Fe(III) (2) Tc(VII) (3).

Fe Tc ,
(NH2NH)2CO, . Tc, 5 ,
Fe. Cr, , .
,

Tc ,
{[HNO3] = 7, [(NH2NH)2CO] = 0.1 , [Tc(VII)] =
1103 /}:
T, C
k, 1

70
0.432

80
1.01

90
1.75


72 /, , Tc.


(NH2NH)2CO , .
( )
d[(NH2NH)2CO]/dt = k0.

(4)

k0
. 2. 2. .
[(NH2NH)2CO] = 0.1 /, 90. k -
1

[HNO3], / [U(VI)], / k, k/k k0, /()


6

0.125

6
0.2

1.20
7
0.3

1.32
7
0.35

1.40
7

0.324 1.82

1.75 9.83

0.144 0.81

0.178

, ,

0.001 / Fe(III), Tc(VII), Cr(III) .

U(VI).
HNO3
. (NH2NH)2CO
(), ,
U(VI) Fe Tc ,
30%.

.
(2)
(3),
(NH2NH)2CO.
, HNO3 +3.5 +3
70 90C. ,
, Np(VI) [3]. ,

HNO3, +3,
, +3, HNO3. , ,
.
HNO3, [4]
d[N2H4]/dt = k[N2H4][HNO3]33

(5)

( HNO3).
[4] , -
NO2+, HNO3
3HNO3 NO2+ + H3O+ + 2NO3,

(6)

[HNO3]3.
,
(NH2NH)2CO HNO3 NO2+, (6).
d[(NH2NH)2CO]/dt = k'K[(NH2NH)2CO][HNO3]3 (7)

[K (6), k'
]
-

142

. . .

(3). ,
NO2+ U(IV) Np(V) [3].
Fe Tc
,
, . , Fe
Fe(III) + (NH2NH)2CO Fe(II) + ,

(8)

Fe(II) + HNO3 Fe(III) + HNO2.

(9)

HNO2 [1] - , -

HNO3.
[4]
k = 1.62103 3/(3) 97C (5)
113.7 / , 1.29 1
90C [HNO3] = 7 /,
N2H4 HNO3.
(NH2NH)2CO HNO3 k = 0.18 1, .. ~7 , , HNO3.

[1] . ., . ., . . . // . 2012. T. 54, N 2. C. 133138.
[2] Kurzer F., Wilkinson M. // Chem. Rev. 1970. Vol. 70, N 1.
P. 111149.
[3] . . . .: , 1974. 312 .
[4] . ., . ., . . // . 1962. . 3, N 6. C. 877881.

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