133

, 2012, . 54, N 2, c. 133138

Pu(IV) Np(VI)

. . a, . . a, . . *a, . . , . . ,
. . a, . . , . .

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

- ,

25.04.2011; 05.10.2011

546.798.21:546.798.22:547.497.1

Pu(IV) Np(VI) (NH2NH)2CO 16 /

HNO3. , Pu(IV) Pu(IV), [HNO3] 3 / .
, . ,
Np(VI) Np(V) , Np(V)
Np(IV) Fe Tc. Pu Np.
: , , , , , , , , , , .

, ,
,
- Pu Np. ,
[1].
(NH2NH)2CO, , , Pu(IV)
Np(VI) .


- [25]. . , Cu2+ Fe3+ Cu+ Fe2+ ,
CO2 N2 [6].
-

.

Pu(IV) Np(VI) HNO3, Pu Np .

.

HNO3 , -

, Pu(IV) Np(VI)

() 350 1100 .
Pu Np
(D) = 475, 602, 980 710 , Pu4+, Pu3+, NpO2+
Np4+ .
. Pu PuO2 HNO3
HF. PuO2 Al(NO3)3
F. 7 /
HNO3
-1. Pu
H2O2.

440 / Pu 6.6 / HNO3.
90 / Np NpO2 ( 98%)
7 / HNO3
Np(VI) Np(IV) Np -1 .

Np(IV) Np(VI)
. Pu
Np - ,

UV-1201 ( Shimadzu).
Tc(VII)
KTcO4

134

. . .

97%. Tc
- .
0.1 / HNO3 97% (Acros Organics, ).

[7].
HNO3 ..
0.1 / , , U Pu
.

. 1. Pu(IV) . [Pu(IV)] = 0.010, [HNO3] = 1,

[(NH2NH)2CO] = 0.05 /; ~10.

Pu(IV)
(<1 /
HNO3) Pu(IV)
Pu(III) 12 , Pu(III) , , 50 / U(VI) 100 / Tc(VII).
(~10C) ,

Pu(IV) (. 1),

d[Pu(IV)]/dt = k1[Pu(IV)],

. 2. Pu(IV) . [Pu(IV)] = 0.012, [(NH2NH)2CO] = 0.2 /; 35.

[HNO3], /: 1 1, 2 4, 3 3 {+ 5103 / [Tc(VII)]},
4 6.

(1)

0.02 1 [HNO3] = 1 /
[(NH2NH)2CO] = 0.05 /.
,
Pu(III) Pu(IV) (. 2).
K = [Pu(III)]/[Pu(IV)]

(2)

{[Pu(III)] [Pu(IV)]
Pu(III) Pu(IV)}
.
[8].
[ Pu(IV)], [ Pu(III)]
Pu, ln[A/(A x)],
A = Ka/(K + 1), a
Pu(IV), x Pu(III) t.

(k1)
(k1) . k1 + k1 K, k1/k1,

. 3. ln[A/(A x)]
Pu(IV) . [Pu(IV)] = 0.012, [(NH2NH)2CO] = 0.2,
[HNO3] = 6 /. T, C: 1 35, 2 50.

. . 3, . 1
k1 k1 .
. 1 ,
HNO3 ,
.
1. (k1)
(k1) Pu(IV) .
[Pu(IV)] = 0.012, [(NH2NH)2CO] = 0.2 /
[HNO3], / T, C [Tc(VII)], / k1, 1 k1, 1
3
35
0.005
0.15
0.020
4
35
0
0.12
0.016
6
35
0
0.011 0.0064
6
50
0
0.054 0.012

 Pu(IV) Np(VI)

135

,
Pu(IV) , . , ~88 ~34 /
.
, 3 / HNO3, Tc, Pu(III)
(. 2).
Np(VI) Np(V)
([HNO3] < 1 /)
Np(VI) Np(V). 0.3 / HNO3
(1015) Np(VI) Np(V)
.
HNO3, ,
1 / HNO3 [(NH2NH)2CO] = 0.05 /
~10 ~8 .
Np(V)
Np(IV), Fe Tc
(. 4).

Np(IV),
.
Np(V) Np(IV)
710 ( Np4+).
, ,
Np
d[Np(V)]/dt = d[Np(IV)]/dt = k[Np(V)].

(3)

ln(D D), D
D . , . 5, ,
k, . 2.
. 2 , Fe Tc Np(V),
Tc(VII) 4 ,
Fe(III). Fe

Fe(III) + (NH2NH)2CO Fe(II) + ,

(4)

Np(V) + Fe(II) Np(IV) + Fe(III).

(5)

-, Tc.

. 4. Np(IV) Np(VI) . [Np(VI)] = 8.4103,

[(NH2NH)2CO] = 0.2, [HNO3] = 3 /. : 1 , 2 9104 / Fe(III), 3 1103 / Tc(VII);
. 5.

. 5. ln(D D) Np(V) . [Np] = 8.4103, [(NH2NH)2CO] =

0.2, [HNO3] = 3 /.

(
) HNO3 Fe k
~4.5 3
6 / HNO3.

Pu Np

Pu Np,
Pu(III)Np(V),
U,
Pu(III)Np(IV),
Pu Np
.
, Pu(III)
Np(V) ([HNO3] 1 /),
Pu(IV), Np(VI) 2. Np(V)
. [(NH2NH)2CO] = 0.2 /, T = 35
[Np]103 [HNO3] [Fe(III)]104 [Tc(VII)]103
k103, 1
/
8.4
3
0
0
0.18
8.4
3
9.0
0
1.15
8.4
3
0
1.0
4.5
4.2
6
9.0
0
5.1

136

. . .

, Pu(III) Np(V)
.1
Pu(III)
Np(V) 35C 1.1 / HNO3, (/): 0.012 Pu(IV), 2.1103 Np(VI) 0.2
(NH2NH)2CO. . 6, Pu(IV) ( 1 ) Pu(III),
Np(VI) ,
Pu, Np(V),
, Np(IV) ( ~30% 5.5 ).

Np(VI) Np(V) Np(V)
Np4+ + NpO22+ + 22O 2NpO2+ + 4H+,

. 6. Pu(III) Np(V)
Pu(IV) Np(VI) . [HNO3] =
1.1, [Pu(IV)] = 0.012, [Np(VI)] = 2.1103, [(NH2NH)2CO] =
0.2 /; 35.

(6)

Np(IV) , ,
NpO2+ + Pu3+ + 4H+ Np4+ + Pu4+ + 22O.

(7)

[9]
(7) 30% () {[Pu(IV)] = 0.012, [Np(VI)] = 8.4103, [HNO3] =
1.1 /, 35} ~3.5 , . , ,
[9] ( = 2), ,


.
, Np(IV) ,
Pu(III)Np(V). ,

(0.5 /) (2025C),
Np(IV) (7) ( [9],
~14 [HNO3] = 0.5 / 25C).
Pu(III)Np(IV) .
Np(V)
Np(IV) , , Np(V) (7),
HNO3 [9]. 1

, Np(V)
HNO3 Fe
, ,
. 2 , 10% Np(V)
Np(IV) 97 [HNO3] = 1, [(NH2NH)2CO] =
0.2 / 35C.

. 7. Pu(III) Pu(IV) Np(VI) . [HNO3] = 6,

[Pu(IV)] = 0.012, [Np(VI)] = 2.1103, [(NH2NH)2CO] = 0.2 /.
T, C: 1 35, 2 50.

HNO3 Pu(IV) Pu(III).

,
. , ,
[ Pu(IV)]

[ Pu(III)] , , , , Pu(IV) Pu(III).
Pu(III)Np(IV)
6 / HNO3 35
50C. Pu(IV) Np(VI)
0.012 2.1103 / , 0.2 /.
,
Pu(IV)
, , , 50C ( 81% 63% 35C) (. 7).
18 Pu(III) ( 25%) Pu(IV).
Np(IV)
1.52
, Pu.
35C Np Np(IV), -

 Pu(IV) Np(VI)

. 8. Pu(III) Np(V)
Pu(IV) Np(VI) . [Pu(IV)] =
0.012, [Np(VI)] = 2.1103, [(NH2NH)2CO] = 0.2, [HNO3] = 3,
[Fe(III)] = 9104 /; 50.

(5 ) 980 , Np(V) ,
~8105 / ( 4% Np).
18 Np(V). 50C Np
Np(IV),
(18 ) 1.5% Np(IV)
.
,
( ~70C)
Pu(IV) Pu(III), Pu(III) , ,
Np(IV) , -,
Pu(III)Np(IV) (67 / HNO3).
Pu(IV) Pu(III)
HNO3,

Pu(III)Np(IV) ,

, Np(V) Np(IV).
HNO3 3 /,

Np(V) 50C. , Fe(III)
(9104 /), . Pu(IV) Np(VI)
, (0.012
2.1103 / ).
Pu(III)
Np(V) . 8. , Pu(IV) Np(V) Pu(III) Np(IV) ~9798% ~1.5
2 , Pu Np
70 .

137

, Pu(IV) (1 /).


, , Pu [1]. [10, 11] ,
[HNO3] = 1 / 35 Pu(IV) 99% 1.3, 3.7, 1.3
1.1 , ,
( 0.5 /).
Pu(III)
(
Tc) , ,
-, Pu(III)
. , HNO2
( ~20C, [(NH2NH)2CO] =
0.1, [HNO2] = 0.014 [HNO3] = 0.5 /
), , ,
HN3. ( 3 / HNO3) Pu(IV) , Pu(III)
,
Tc(VII).
, ,
Np(VI) Np(V) (<1 /),
(
~3 / HNO3) Np(V)
Np(IV), Fe
Tc.

Pu(III)Np(V) (1.1 / HNO3) - Np(IV), Np(V) Pu(III). ,
Pu(III)Np(V) (<1 / HNO3) (~2025C), .

Pu(III)Np(IV) 3 / HNO3 50C
[ 50 / Fe(III)]
~98% Pu Np
, .

. . .

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