, , ( ). f- , , , .. La Lu; Th Lr. 3+ 2 f-. , (), - , . , , , . , La3+ < 3+ < Pr3+ << Dy2+ < Y3+ < 3+< < Lu3+ <Sc3+.
(, , ). Ln(NO3)3-. , . , . ~ 2,5. , .
, , - .
3C(NO3)3 + KMnO4 + 3H2O = 2C(NO3)4 + C(OH)4 + KNO3 + H2MnO3
C(NO3)4 + 4H2O = C(OH)4 + 4HNO3;
Yb(CH3COO)3 + Na(Hg)n = Yb(CH3COO)2 + CH3COONa + nHg
Yb(CH3COO)2 + 2Na(Hg)n = Yb(Hg)n + 2CH3COONa
(Th,U,Pu.) - - . , ~ 50 /2, ( Lu d. = 9,85 /c3). (11-20 /3). f - . (Gd, Sm, Eu, Dy) .
, Tm, , , 1,39 * 104; 4,5 * 109 24360 .
.4.5.
.
R ., | , /3 | J ., | : + + - = , | T .., 0C | , % | ||
Ce | 0,182 | 6,79 | 5,47 | -2,483 | 7*10-3 | 1,08 | |
Pr | 0,183 | 6,77 | 5,42 | -2,462 | 9*10-4 | 1,07 | |
Nd | 0,182 | 7,01 | 5,49 | -2,431 | 3,7*10-3 | 1,07 | |
Pm | - | 7,22 | 5,55 | -2,423 | - | 1,07 | |
Sm | 0,180 | 7,52 | 5,63 | -2,414 | 8*10-4 | 1,07 | |
Eu | 0,204 | 5,24 | 5,66 | -2,407 | 1,3*10-4 | 1,01 | |
Gd | 0,180 | 7,89 | 6,16 | -2,397 | 8*10-4 | 1,11 | |
Tb | 0,178 | 8,23 | 5,85 | -2,391 | 4,3*10-4 | 1,10 | |
D | 0,177 | 8,55 | 5,93 | -2,353 | 5*10-4 | 1,10 | |
Ho | 0,177 | 8,79 | 6,02 | -2,319 | 1,7*10-4 | 1,10 | |
Er | 0,176 | 9,06 | 6,10 | -2,296 | 3,3*10-4 | 1,11 | |
Tm | 0,175 | 9,32 | 6,18 | -2,276 | 2,7*10-5 | 1,11 | |
Yb | 0,194 | 6,96 | 6,25 | -2,267 | 3,3*10-5 | 1,06 | |
Lu | 0,175 | 9,84 | 6,15 | -2,255 | 8*10-5 | 1,14 |
|
|
.4.6.
R ., | , /3 | J ., | : + + - = , | T .., 0C | , % | ||
Th | 0,180 | 11,72 | 6,08 | -1,899(Th4+) | 1,3*10-3 | 1,11 | |
Pa | 0,162 | 15,37 | 5,89 | -1,46(Pa+4) | 1*10-10 | 1,14 | |
U | 0,153 | 18,95 | 6,19 | -1,780 | 2,5*10-4 | 1,22 | |
Np | 0,150 | 20,25 | 6,20 | -1,856 | 1,22 | ||
Pu | 0,158 | 19,84 | 6,06 | -2,031 | 1,22 | ||
Am | 0,184 | 13,67 | 5,99 | -2,32 | - | 1,20 | |
Cm | - | 13,30 | 6,09 | -2,06 | - | 1,20 | |
BK | - | 14,79 | 6,30 | -1,05 | - | 1,20 | |
Cf | - | 15,0 | 6,30 | -1,93 | - | 1,20 | |
Es | - | - | 6,42 | -2,0 | - | 1,20 | |
Fm | - | - | 6,50 | -1,96 | - | - | 1,20 |
Md | - | - | 6,58 | -1,7 | - | - | 1,20 |
No | - | - | 6,64 | -1,2 | - | - | 1,20 |
Lr | - | - | 6,75 | -2,06 | - | - | 1,20 |
BK Lr , .
- . , .. .
. 150-180 . - , ( ). , I - 222,4 . - :
4Ln + 3O2 = 2Ln3O3 = -1600
Ln2O3, l2, Pr Pr6O Tb - Tb4O7.. Ln2O3 , , . .
Ln2O3 + 3 H2O = 2Ln(OH)3
Gd2O3 + 6HNO3 = 2Gd(NO3)3 + 3 H2O
2 - , . , , ( ). Pa2O5, UO3 . , :
|
|
Pa2O5 + H2SO4 = (PaO2)2SO4 + H2O
UO3 +2HCl = UO2Cl2 + H2O
(+5) (+6) , 2+ 22+ (Pa2+ , UO22+ - , NpO22+ - ..). (, , ) S - :
2UO3 + K2CO3 = K2U2O7 + CO2
K2U2O7 + K2CO3 = 2K2CO4 + CO2
200 , LnCl3, LnBr3, LnJ3, - . , LnF3 , . LnF3 * nH2O:
LnF3 * nH2O LnF3 + nH2O
.
, , (F6). . 235UF6 238UF6.
Th, Pa, U, Np ( )
2HCl3 + 4H2O = 2U(OH)2l2 + 2 + 2l
450 , Ln2S3 ( LnS, Ln5S7, Ln3S4, LnS2). 20000. , , , .
f :
a.
b.
B, C, Si, N, P, Se, Te , . , , , US, .
. ( ). La , . . Ln(OH)3 - . Ln(OH)3 . C (OH)4, C(OH)3
4C(OH)3 + O2 + 2H2O = 4C(OH)4
:
2NaOH + C(OH)4 = Na2CO3 + 3H2O
Eu(OH)2, Sm(OH)2, Yb(OH)2
. ()4 . 2()2, 2(), :
PaO2(OH) + HCl = PaO2Cl + H2O
UO2(OH)2 + 2HNO3 = UO2(NO3)2 + 2H2O
3 24, :
24 + 2 = 24 + 2H2O
(+6), (+6), (+6) .
UO2(NO3)2 + 2H2O = UO2(OH)2 + 2HNO3
. , :
2Dy + 6HClO4 = 3H2+ 2Dy(ClO4)3
Eu + 2HJ = H2+ EuJ2
- (HNO3, H2SO4, HClO3) .
8La + 3HNO3 = 8La(NO3)3 + 3N2O + 15H2O
10Eu + 36HClO3 = 10Eu(ClO3)3 + 3Cl2 + 18H2O
|
|
U + 4HNO3p = UO2(NO3)2 + 2NO + 2H2O
H2SO4 , - Ln2(SO4)3.
() () :
f-
. . , . LnH3. , . LnH3 , :
LnH3 + 3H2O = Ln(OH)3 + 3H2
ClH3 ClH2
2ClH3 2ClH2 + H2 2Cl + 3H2
(Th, U ) . UH(3-x), PuH(2-x), , .
2U + 3H2 = 2UH3
2ThH3 + 32 = 2Th(OH)3
.
. (+3) LnCl3, Ln(NO3)3, Ln2(SO4)3, LnF3, Ln2(3)3, Ln4. , , [Nd(H2O)6](NO3)3, [Nd(H2O)8](BrO3)3. [(H2O)n]3+ (+3). , f- . , . . (Br -,Cl -,J -,NO-3) e , , Ln3+ , , . , . 10+14 ( La - 8+9), 4f - .
2[UCl6], [UO2(H2O)6]SO4.
- . , Ln2+. Eu(2+) Sm(2+).
2SmCl + H2 = 2SmCl2 + 2HCl
EuJ3 = EuJ2 + 1/2J2
( = -0,33B), (+2) ( = -2,9/-1,15B).
2SmCl2 + 2H2O = 2SmCl + H2 + 2HCl
(+4) K2CeF6, Ce(ClO4)4, Ce(SO4)2 ( = 1,61B).
2Ce(SO4)2 + 2HCl k = Cl2 + Ce2(SO4)3 + H2SO4
. Th(+3), Pa(+3), U(+3), Np(+3) , (+5, +6, +7.) (AmO2, UO2(NO3)2, Ba3(NpO5)2) .
2AmO2F + 2H2O2 + 3H2SO4 = Am2(SO4)3 + 3O2 + 2HF + 4H2O
2NpO2Cl2 + SnCl2 = 2NpO2Cl + SnCl4
, d- .
Pa2O5 + H2SO4 = (PaO2)2SO4 + H2O
, , . . 0,03% .
|
|
. , . , . , Fe, n , .
Sm, Eu Gd , 170Tm , 5 . 170m - .
, 2 , La Lu - , Ag Cu . ,
,
, , , . . 235U ~75 I . .
1. f- .
2. : ) , , ) (+3), ) (+4).
3. , : ) (+2), ) (+3), ) (+4). .
4. - (+2) (+4).
5. - (+2, +3, +4). .
6. ²² ?
7. :
8.
Ce(OH)3 + O2 + H2O =
Ce2O3 + NaBiO3 + HNO3 =
Ce(OH)4 + HCl (k) = CeCl3 +
CeO2 + H2O2 + HNO3 = O2 +
(+3) (+4) ?
8. 89,96 103. , .
9. PuO2+ :
PuO2+ + H+ = PuO22+ + P3+
10. , +5 +6 2+ 22+?
, , , , , .
, , , .. , . .., , .
, , . , , , , , .
.
|
|
E0,B | ||
Cu | Cu+ + e- =Cu | 0,52 |
Cu+2 +2e- =Cu | 0,34 | |
Ag | Ag+ +e- =Ag | 0,80 |
Au | Au+ + e- =Au | 1,69 |
Au+3 +3e- =Au | 1,498 | |
u + 2CN - - - = [u(CN)2]- | -0,01 | |
Zn | Zn+2 +2e- =Zn | -0,76 |
Cd | Cd2+ +2e- =Cd | -0,40 |
Hg | ||
Sc | Sc+3 +3e- = Sc | - 2,08 |
Y | Y +3 +3e- = Y | - 2,37 |
La | La +3 +3e- = La | - 2,52 |
Ac | Ac +3 +3e- = Ac | - 2,6 |
Ti | Ti +4 +4e- = Ti | |
Ti +3 +3e- = Ti | - 1,63 | |
TiO2+ + 2H+ +e- Ti3+ +H2O | 0,10 | |
Zr | Zr +4 +4e- = Zr | - 1,56 |
Hf | Hf +4 +4e- = Hf | - 1,70 |
V | V2+ +2e-= V | - 1,18 |
V3+ +3e-= V | - 0,87 | |
HVO3+ 3H++e- VO2+ +2H2O | 0,92 | |
Nb | Nb3+ +3e-= Nb | - 1,10 |
Cr | CrO42+ 8H+ +6e- Cr0 +4H2O | 0,336 |
Cr2O72-+14H++6e-2Cr3+ +7H2O | 1,33 | |
O42-+8H++6e- 0 +4H2O | 0,154 | |
WO42-+ 8H+ +6e- W0 +4H2O | 0,049 | |
MnO4-+ 8H++5e- Mn2+ +4H2O | 1,51 | |
Fe | Fe2+ +2e-= Fe | - 0,441 |
Fe3+ +3e-= Fe | - 0,036 |
2
25 0
. | ||
[Cu(CN)2]- | 1×1024 | |
[Ag(CN)2]- | 7×1019 | 1,1×10-21 |
[Au(CN)2]- | 2×1038 | |
[CuCI2]- | 2×105 | |
[CuBr2]- | 8×106 | |
[CuI2]- | 7×108 | |
[Ag(N3)2]+ | 9,3×10-8 | |
[Ag(N2)2]- | 1,8×10-3 | |
[Ag(S2O3)3]3- | 1,1×10-13 | |
[HgCI4]2- | 8,5×10-16 | |
[HgBr4] 2- | 1,0×10-21 | |
[HgI4]2- | 1,5×10-30 | |
[Hg(CN)4]2- | 4,0×10-42 | |
[Cd(N3)2]+2 | 7,6×10-8 | |
[Cd(CN)4]2- | 7,8×10-18 | |
[Cu(N3)4]2+ | 2,1×10-13 | |
[Cu(CN)4]3- | 5,0×10-31 | |
[Ni(N3)6]+2 | 1,9×10-9 | |
[Zn(OH)4] 2- | 7,0×10-16 | |
[Zn(N3)4]+2 | 2,0×10-9 | |
[Zn CI4]2- | ×10-16 | |
[Cd CI4]2- | ×10-16 | |
[Cd I4]2- | ||
[Zn I4]2- |
:
1. .. : . .... .- .:, 2001-368.
2. .. . .: , 2001.-743.,.
3. .. .: -,2002.
4. .. .- .: ,2002.
5. , , .[] / .. .- : - ,1987.-503.
6. : /.. ..- .:..,2003.-255.