Download - Lantanidi i Actinidi
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f-
19-20
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3 Sc Y La Ac
. 21 39 57 89
. 44.956 88.906 138.905 [227]
. . 3d14s2 4d15s2 5d16s2 6d17s2
R(.), 164 181 187 203
I1, 6.54 6.38 5.58 5.17
I2, 12.80 12.24 11.06 12.13
I3, 24.74 20.52 19.18 19.70
(A-R) 1.20 1.11 1.08 1.00C.O. 3 3 3 3
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Sc Y La Ac
.., 1539 1522 920 1050
.., 2831 3260 3420 3300
d, /3 3.02 4.47 6.12 10.06
E0(M3+/M0), 2.03 2.37 2.25 2.13
-Sc -Sc-Y -Y-La -La -La
1336 oC
1480 oC
260 oC 880 oC
-Sc, -Y, -La: Mg-Sc, -Y, -La, Ac: Cu
-La: -Fe
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1.
2Sc + 6HCl = 2ScCl3 + 3H22Y + 3H2SO4 = Y2(SO4)3 + 3H2
2. Sc
2Sc + 6NaOH + 6H2O = 2Na3[Sc(OH)6] + 3H23. La, Ac
2La + 6H2O = 2La(OH)3 + 3H24. , , ,
2Sc + 3Cl2 = 2ScCl3 Y + P = YP
2La + N2 = 2LaN 2La + 3S = La2S3
E0(Sc3+/Sc0) = 2.03
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Sc, Y, La, Ac
1. M2O3 M(OH)32.
3.
Sc(OH)3 Y(OH)3 La(OH)3 Ac(OH)3
4.
Sc2O3 + 6HNO3 = 2Sc(NO3)3 + 3H2O
Y(OH)3 + 3HCl = YCl3 + 3H2O
La(OH)3pKb = 3.3
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Sc, Y, La, Ac
5.
[Sc(H2O)6]Cl3 [Sc(OH)(H2O)5]Cl2 + HCl6. +3
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Y(NO3)3 + 3NaF = YF3+ 3NaNO37. , , ,
, , , . .
8. ..
ScCl3 + Sc = Sc2Cl3 10Sc2Cl3 + Sc = 3Sc7Cl10
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Sc
1. 3
2. ,
Sc(NO3)3 + 6KOH = K3[Sc(OH)6] + 3KNO33.
2ScCl3 + 3Na2CO3 + H2O = 2Sc(OH)CO3 + CO2 + 6NaClSc(OH)CO3 + 3Na2CO3 = Na5[Sc(CO3)4] + NaOH
4. : Sc2(C2O4)3
Sc2(C2O4)3 + 6HCl + 6NaF = 2ScF3 + 6NaCl + 3H2C2O42ScF3 + 3Ca = 2Sc + 3CaF2
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f-
4f-
5f-
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f-
1. f- n2
2. : +3 , Ce+4, Eu2+
3. : La Lu ( )
4. : , .. +2 +7
5. , Pm
6. f-
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f-
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LnM M0 M3+ ..Ln [Xe]5d16s2 [Xe] 3Ce [Xe]4f15d16s2 [Xe]4f1 3, 4Pr [Xe]4f36s2 [Xe]4f2 3, 4Nd [Xe]4f46s2 [Xe]4f3 2, 3Pm [Xe]4f56s2 [Xe]4f4 3Sm [Xe]4f66s2 [Xe]4f5 2, 3Eu [Xe]4f76s2 [Xe]4f6 2, 3Gd [Xe]4f75d16s2 [Xe]4f7 3Tb [Xe]4f96s2 [Xe]4f8 3, 4Dy [Xe]4f106s2 [Xe]4f9 3Ho [Xe]4f116s2 [Xe]4f10 3Er [Xe]4f126s2 [Xe]4f11 3Tm [Xe]4f136s2 [Xe]4f12 2, 3Yb [Xe]4f146s2 [Xe]4f13 2, 3Lu [Xe]4f145d16s2 [Xe]4f14 3
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100120140160180200
Ln0
Ln3+
R,
La Pr Pm Eu Tb Ho Tm Lu Ce Nd Sm Gd Dy Er Yb
Ln
-
Ln
-2,4
-2,3
-2,2
-2,1
-2,0
800
1000
1200
1400
1600
1800
Ln
Ln
E(M3+/M0),
T.., 0
Eu
Eu Yb
Yb
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Ln1. LaLu2.
2Ho + 3H2SO4 = Ho2(SO4)3 + 3H23.
Nd + 3H2O = Nd(OH)3 + 3H24.
4Gd + 3O2 = 2Gd2O3Ce + O2 = CeO212Pr + 11O2 = 2Pr6O118Tb + 7O2 = 2Tb4O7
CeO2
Lu(OH)3
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Ln5.
Ce + 2F2 = CeF42Er + 3Cl2 = 2ErCl3
6. , , , , ,
2Tb + 3Se = Tb2Se3 Nd + 5P = NdP52Gd + 3H2 = 2GdH3 La + 2C = LaC2Yb + H2 = YbH2
7. 2Sm + 2NH3 = 2SmN + 3H2
8. Pr + 18NH3 () = [Pr(NH3)6]2+ + 2[e(NH3)6]
NdCl3
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Ln
1. Ln2O3 Ln(OH)3
2. La(OH)3 Lu(OH)33. , , .
4Nd(NO3)3 = 2Nd2O3 + 12NO2 + 3O2 (t0)La2(SO4)3 = La2O(SO4)2 + SO2 + O2 (t0)
4. , , Dy2(CO3)3 = Dy2O2(CO3) + 2CO2 ~500 0CDy2O2(CO)3 = Dy2O3 + CO2 ~800 0C
5. Gd2O3 + 3C + 3H2S = Gd2S3 + 3H2 + 3CO
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6. SmCl3 + 3NaC5H5 = Sm(C5H5)3 + 3NaClSm(C5H5)3 + 3FeCl2 = Fe(C5H5)2 + 2SmCl3
7. (
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(III)
1. fn
2. M-L
3.
4. LaLu
:
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Ce(IV)
1. CeO2.. 2400 0,
2. Ce + O2 = CeO2Ce + 2F2 = CeF44Ce(OH)3 + O2 + 2H2O = 4Ce(OH)4
3. Ce(OH)4 CeO2xH2O Ce(SO4)2 + 4KOH = Ce(OH)4 + 2K2SO4Ce(OH)4 + 2H2SO4 = Ce(SO4)2 + 4H2OCeO2 + 2NaOH = Na2CeO3 + H2O (t0)
4. 2Ce(OH)3 + 3H2O2 = 2Ce(OH)3(OOH) + 2H2O
CeO2
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Ce(IV)
5. Ce(IV) 6Ce(SO4)2 + 8H2O = Ce6O4(OH)4(SO4)6 + 6H2SO4
6. Ce(IV) Ce(OH)4 + 4HNO3 + 2NH4NO3 = (NH4)2[Ce(NO3)6]2CeCl3 + Cl2 + 4HCl = 2H2[CeCl6]Ce(OH)4 + 5Na2CO3 = Na6[Ce(CO3)5] + 4NaOH
7. Ce(IV) 2Ce(SO4)2 + 2KI = Ce2(SO4)3 + K2SO4 + I2
8. E0(Ce4+/Ce3+) = 1.72 1M HClO4E0(Ce4+/Ce3+) = 1.61 1M HNO3E0(Ce4+/Ce3+) = 1.44 1M H2SO4 [Ce(CO3)5]6
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Eu(II)1.
Eu2(SO4)3 + Zn = 2EuSO4 + ZnSO4 -2EuCl3 + 3H2 = 2EuCl2 + 6HCl (t0)
2. EuO .. 1980 0, NaCl
Eu2O3 + Eu = 3EuO (t0)Eu2O3 + H2 = 2EuO + H2O (t0)
EuO + H2O = Eu(OH)2
3. : E0(Eu3+/Eu2+) = 0.35 2EuSO4 + Fe2(SO4)3 = Eu2(SO4)3 + 2FeSO4
4. Eu(II) Ca(II), Sr(II), Ba(II)
EuSO4
EuCl2
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(II)
E
0
(
M
3
+
/
M
2
+
)
,
R
(
M
2
+
)
8
,
Nd
Sm
Eu
Dy
Tm
Yb
f14
f13f10
f7
f6
f4
-3
-2
-1
1.0
1.1
1.2
1.3
Ln(II), Eu(II) Yb(II)
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:1. Ce(IV)2. Eu(II)3.
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YAG
La/Ce Nd-
SrAl2O4:EuEu-Y-
Sc, Y, Ln
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Z
Ac 89 227Ac 22 1899Th 90 232Th 1010 1828Pa 91 231Pa 30000 1917U 92 238U 4.5109 1789
Np 93 237Np 2106 1940Pu 94 244Pu 8107 1940Am 95 243Am 7000 1944Cm 96 247Cm 1.5107 1944Bk 97 247Bk 1400 1949Cf 98 251Cf 890 1950Es 99 252Es 471 1954Fm 100 257Fm 101 1954Md 101 258Md 56 1955No 102 259No 58 1958Lr 103 262Lr 3 1961
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0 [Rn] M3+[Rn]
.. 0 [Rn] M3+[Rn]
..
Ac 6d17s2 5f0 3
Th 6d27s2 5f1 (2),3,4 Bk 5f97s2 5f8 (2),3,4
Pa 5f26d17s2 5f2 3,4,5 Cf 5f107s2 5f9 2,3,(4)
U 5f36d17s2 5f3 3,4,(5),6 Es 5f117s2 5f10 2,3
Np 5f46d17s2 5f4 (3),4,5,6,7 Fm 5f127s2 5f11 2,3
Pu 5f67s2 5f5 3,4,5,6,7 Md 5f137s2 5f12 2,3
Am 5f77s2 5f6 2,3,4,5,6,(7) No 5f147s2 5f13 2,3
Cm 5f76d17s2 5f7 (2),3,4,(5) Lr 5f146d17s2 5f14 3
An
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80100120140160180200
An0
An3+
Ac Pa Np Am Bk Es Md LrTh U Pu Cm Cf Fm No
R,
An
-
600
800
1000
1200
1400
1600
1800
10
12
14
16
18
20
22
..,
, /3
Ac Pa Np Am Bk
Ac Pa Np Am Bk
Th U Pu Cm Cf
Th U Pu Cm Cf
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1. f- 5-
2. 5f 6d
3.
4. Th Cm
5. +3
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1.
2. 4f- , 5f-
3. d- : ..
Sc Ti
Y Zr
Hf
Th
La
Ac
V Cr Mn Fe Co Ni
Nb Mo Tc Ru Rh Pd
Ta W Re Os Ir Pt
Pa U Np Pu Am (Cm)
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1. Cm. Lr .
2. Th U
3. , .
4. .
5. .
6. .
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7. . 2Ac + 6H2O = 2Ac(OH)3 + 3H2
8. Pa ,
4Pa + 5O2 = 2Pa2O5 (to) PaV
2Pa + 5Br2 = 2PaBr5 (to) PaV
2Pa + 3H2 = 2PaH3 (to) PaIII
9. .. Np (+7)
3K3[NpVIIO4](OH)2] + K3[Cr(OH)6] = 3K2NpVIO4 + K2CrO4 + 4KOH + 4H2O
PaBr5
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1. Th U 2.
:238
92U + 10n = 23993Np + e-
-:253
99Es + 42He = 256101Md + 10n
:238
92U + 126C = 24698Cf + 410n
1912-1999
1913-1990
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Th , (0.0001 .%) : (Ln,Th)PO4, Th(SiO4)2
(Ln,Th)PO4 Th(SO4)2 + Ln2(SO4)3
Th(OH)2SO4
Th ThCl4 Th(OH)4
H2SO4, H2O
NH3H2O
1) H2C2O4 2) NaOH
Ca HCl
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U 2 , Th
K2O2UO3V2O53H2O U3O8
2U3O8 Na4[UO2(CO3)3]
Na4[UO2(CO3)3] (NH4)2U2O7
(NH4)2U2O7 UO2 UF4
UF4 + 2Mg = 2MgF2 + U (to)
Na2CO3 + O2
1) H2SO4 2) NH3
to HF
U3O8
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1.
Th + 4HCl = ThCl4 + 2H2Th + HNO3 ()
2. Th + O2 = ThO2 ThIV
Th + 2Cl2 = ThCl4 ThIV
Th + 2I2 = ThI4 ThIV
Th + H2 = ThH2 ThII
ThO2ThH2
ThCl4
ThBr4
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1.
Th(OH)4 = ThO2 + 2H2O .. = 3220
2. ThIV
ThCl4 + 4NH3H2O = Th(OH)4 + 4NH4Cl = 1042
Th(OH)4 + 4HNO3 = Th(NO3)4 + 4H2O
Th(OH)4 + 2H2SO4 = Th(SO4)2 + 4H2O
3. ThIV ,
Th(NO3)4 + 8H2O [Th(H2O)8]4+ + 4NO3Th(OH)4 + CO2 = ThOCO3 + 2H2O
4.
4Th(NO3)4 + 6H2O2 + 2H2O = Th4O14 + 16HNO3
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ThF4 ThCl4 ThBr4 ThI4
. . . .., 1070 770 678 566.., 1680 920 880 837fH0298, /
482 285 227 160
..
8 8 8 8
. = 1025
ThF4 () + NH4F (-) = (NH4)3[ThF7] ZrThF4 () + NH4F (-) = (NH4)4[ThF8] HfThCl4 + 2KCl = K2[ThCl6]
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.. = 7Th(NO3)4 + 3KNO3 = K3[Th(NO3)7]
.. = 8Th(NO3)4 + 4(NH4)2C2O4 = (NH4)4[Th(C2O4)4] + 4NH4NO3
.. = 92Th(OH)4 + 2H3PO4 + NaH2PO4 = Na[Th2(PO4)3] + 8H2O
.. = 10ThOCO3 + 4Na2CO3 + H2O = Na6[Th(CO3)5] + 2NaOHTh(OH)4 + 5Na2CO3 = Na6[Th(CO3)5] 4NaOH
.. = 20ThCl4 + 4Na(cp) = Th(cp)4 + 4NaCl
[Th2(PO4)3]
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(IV)
1.
3ThI4 + Th = 4ThI3 , 700
15ThBr4 + 9Th = 4Th6Br15 , 850
15ThBr4 + 9Th + 4Fe = 4Th6(Fe)Br152.
2Th + 3S = Th2S3
3. ThIV
2Th(SO4)2 + 2HN3 = Th2(SO4)3 + 3N2 + H2SO4 ThIII
Th6(Fe)Br15
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1.
3U + 4O2 = U3O8 ..U + 2H2O = UO2 + 2H2 200 2U + 3H2 = 2UH3 (to)
2. U + F2 = UF6 UVI
U + 5/2Cl2 = UCl5 UV U + 2Br2 = UBr4 UIV
U + 3/2I2 = UI3 UIII
3. U + 4HCl = UCl4 + 2H2 UIV
U + 4HNO3 = UO2(NO3)2 + 2NO + 2H2O UVI
UO2Br
UO2(NO3)2
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(VI)1. UF6
UF6 + H2O = UOF4 + 2HF
2. UVI
3U3O8 + 20HNO3 () = 9UO2(NO3)2 + 2NO + 10H2O
3U3O8 + 18HCl + 2HNO3 = 9UO2Cl2 + 2NO + 10H2O
3. UVI
UO2(NO3)2 + 2H2O2 = UO2(O2)H2O + 2HNO3
[UO2(H2O)6]2+
d(UO) = 188 , d(UO) = 223
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4. UVI
UO2(NO3)2 + 2NaOH = UO2(OH)2 + 2NaNO3 = 1022
UO2(OH)2 = UO3 + H2O 420
UO3 + H2O = UO2(OH)2 , ..2UO2(NO3)2 + 6KOH = K2U2O7 + 4KNO3 + 3H2O
K2U2O7 + 4HCl = 2UO2Cl2 + 2NH4Cl + H2O
(VI)
U2O72- Rb2U2O7
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(VI) UVI d-
Rb2U2O7 + 6Rb2CO3 + 3H2O = 2Rb4[UO2(CO3)3] + 6RbOHUO2(CH3COO)2 + Zn(CH3COO)2 = Zn[UO2(CH3COO)3]2
, 3Zn[UO2(CH3COO)3]2 + 2NaCl + 6H2O =
2NaZn[UO2(CH3COO)3]36H2O + ZnCl2
K2U2O7 + 10KNCS + 3H2O = 2K3[UO2(NCS)5] + 6KOH
[UO2(CO3)3]4
[UO2(NCS)5]3
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..1. U3O8 + 2CO = 3UO2 + 2CO2 U3O8 + 2H2 = 3UO2 + 2H2O
UO2 -, .. = 2775 2. UIV
UO2 + 4HF = UF4 + 2H2O , = 61022, ..=1309 UO2SO4 + Zn + 2H2SO4 = U(SO4)2 + ZnSO4 + 2H2OU(SO4)2 + 4KOH = U(OH)4 + 2K2SO4 = 1052
U(OH)4 3. UIV
5U(SO4)2 + 2KMnO4 + 2H2O = 5UO2SO4 + K2SO4 + 2MnSO4+ 2H2SO4
2U(SO4)2 + H2O U2(SO4)3 + O2 + H2SO4a
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1. = 0
UO22+ U4+ U3+ U0+0.33 0.61 1.80
0 1 2 3 4 5 6-6-5-4-3-2-1012
2. = 0
Cr
W
U
Mo
nE
n
Red/Ox
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1. Pu -,
2Pu + 6HCl = 2PuCl3 + 3H2
Pu3+
2. Pu ..
Pu + 3K2S2O8 + 4H2O = K2PuO4 + 2K2SO4 + 4H2SO4 PuVI
Pu + O2 = PuO2 (to) PuIV
2Pu + 3Cl2 = 2PuCl3 (to) PuIII
Pu + H2 = PuH2 (to) PuII
3. +3 +4
PuCl3
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(2011) (1986)
An
f-