VIII . u Ag . :
Ru Rh Pd
5s24d6 5s24d7 5s04d10
Os Jr Pt
6s25d6 6s25d7 6s15d9
, .
:
+6 ,+3, +2, +3, +2 +3, +2
Ru Rh Pd
+8,+6 ,+4, +3 +3 +4 +2,+4
Os Jr Pt
+8, +6,+4 +4, +3 +2 ,+4, +6
: 6 4.
B , . , Au, Cu, Ni . Os Jr (70-90%) Pt . Pt Pd. :
RuS2- , PtS- , Pd3Sb- , (Pt,Pd,Ni)S- .
- Ni .
. 1×10-7 1×10-9 .%. . (1750), 1884 , ., (Ruthenia - ).
- Pt- (SPt =0,2 \1 ). . . , Fe, Ni , Pt- 2[16]. Pt- .
Pt- - . , Ni. Pt- 60 %. ( Pt- Pd). , H2PtCI6; H2PdCI6; H3RhCI6. OsO4. : Pt, Pd, Jr, Rh, Ru.
- , . d - - , Os . , , . Pd Pt . Jr- . Ru Os . C - , , .
H x .
T 3.11
x
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R ., | , /3 | J ., | : 2+/, | T .., 0C | , .% | ||
Ru | 0,134 | 12,4 | 7,36 | - | 9×10-7 | 1,42 | |
Rh | 0,134 | 12,4 | 7,46 | - | 2×10-7 | 1,45 | |
Pd | 0,137 | 12,0 | 8,33 | 0,99 | 2×10-7 | 1,32 | |
Os | 0,135 | 22,5 | 8,7 | - | 5×10-7 | 1,52 | |
Jr | 0,135 | 22,4 | 8,7 | - | 2×10-9 | 1,55 | |
Pt | 0,138 | 21,5 | 9,0 | 1,2 | 5×10-8 | 1,44 |
.
, .
:
(d=12\3) Ru, Rh, Pd
(d=22\3) Os Jr Pt
. 1 Pd 850 2, Pt- 100 . .
x . x . .
. ( ) .
, .
Os + 4F2 OsF8 Os + 2F2 OsF4
Pt- . Os Os4.
:
x , :
Ru + 2KOH +3KNO3= K2RuO4 +3KNO2 + H2O,
Os + 2KOH +4K2SO4= K2OsO5 +4 K2SO3 + H2O,
.
B OsO4.
Rh Ir x . NaCI:
2Rh + 6NaCI +3CI2= 2Na3[RhCI6]
Ir + 2NaCI + 3CI2= 2Na2[IrCI4]
x x ( ) :
3 Pd + 8HNO3 = 3Pd(NO3)2 + 2NO + 4H2O,
Pt- ( ):
3Pt+ 18HCI +4HNO3 = 3H2[ PtCI6] +4NO + 8H2O,
(x)
Pt Pd HCI NCI :
Pt + 2HCI + 2CI2 = H2[PtCI6]
, :
Pt + 6KCN + 4H2O K2[Pt(CN)6] + 2H2 + 4KOH
x .
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. . : (Pt Pd), 23 (Rh, Pt, Jr), 2 ( ), 4 (Ru Os).
, x Os4 Ru4 . , , . K :
Os4 + 2 NaOH = Na2[OsO4(OH)2 ]
O , .
Ru2, , (6000). Os2, Os4. P +4 Ru Os , Os2 :
2Os2= Os + Os4,
Ru2 x x . , +8, +4.
x. (OH)4 x :
2l6 + 6NaOH = (OH)4 + 6NaCI + 2H2O
, Pt(OH)4 :
2[Ptl6] + 8NaOH = Na2[Pt ()6 ] + 6NaCI + 2H2O
Jr (OH)4, Jr2× n H2O JrI4:
JrI4 + 2H2O = ()4 + 4I
- x . , , , +3. +4, x .
x - Rh2O3. Rh2O3 5H2O - , , x, x.
Jr2O3 . Na3[JrCl6] . Jr2O3 n H2O(n→3). .
~1000 0C Jr2. C Jr(OH)4 :
2 Na3[JrCl6 ] + 6NaOH+H2O+ O2= 2Jr(OH)4 + 12Nal
(IV) x, x.
Pd. . x. Pd(OH)2, Pd(NO3)2, x. 8150: 2Pd =2 Pd + 2.
Pd(OH)4, 2000C x PdO.
. . , :
Na2[PtCI4] + 2NaOH = Pt(OH)2 +4NaCI
, , x : 2Pt+2 → Pt 0 + Pt +4, - PtO2 n H2O. .
(+2) x.
, (+3), H[Pt(SO4)2] NaOH.
e (+3) (+4) ( ) (lV) x x :
Pt(OH)4 + 2NaOH = Na2[Pt(OH)6 ]
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Pt(OH)4 + 6HCI = H2[PtCI6 ] + 4 2
, Ru→Rh→Pd Os→Ir→Pt ee ee e ee e, ex ee x x x. ex x e x ee ee e, e e B-.
. x F-Cl-Br-I . x, x . , F3 , F4, F5, F6 x , (F2 , F3 , F4), F8.
X x x x .
JrCI4, OsCI4, RuCI4, PdCI2, PtCI4, x , x :
RuCI4 + 2 = RuOHCI3 + l
Osl4 + 4 2 = Os(H)4 + 4l
OsCI4 RuCI4, RhCI3 x x , ..=6, :
RhCI3 +3 NH4l→(NH4)3[RhCI6]
. x . x x : CN-, CNS-, CH3COO-, , =4,6. , - .
X , : Ru(CO)5; Os(CO)5; - -RhCI2(CO)3. - . 400 = 200-3000. Pt Pd .
Pt- : 2[RuCI6], 3[RuCI6], Na2[OsCI6], 2[PtCI4], 2[PtCI6], .
, x Pd Pt (+2) x : [Pt(NH3)4][PtCI4], [Pd(NH3)4][PdCI4].
NO2- :
2[PtCI6] + NO2 + 2 = 2[PtCI3(NO2)] + NO3 + 31
. Pt- : 2[Pt+2 (CN)4]:
Rh(OH)3 + 6HCN +3KOH = K3[Rh (CN)6] + 6 H2O
K3[Jr(CN)6]- , , .
Pt- :
2[PtCI6] + 6NS = 2[Pt(CNS)6] + 6 KCI
:
2[PtCI4] + 2 NH3 [Pt(NH3)2CI2] + 2 KCI.
e-e xe ee. Ru4, Os4, PdO2 - e . Ru4 , e ee , :
2Ru4 +2 2 = 22Ru4 + 2
Ru4 +101 = 2[Ru16 ] + 212 + 2
OsF8, x :
OsF8 + 42 = Os4 + 8F
(+4) , :
Pt14 + 22S = Pt + 2S + 4HCI.
PdCI2, :
PdCI2 + + 2 = Pd + C2 + 21
(~70%) Pt, Pd, Rh . , . 10% - , 1600 .
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. . ( ) . , , , , , , , .
. , , , .
. , ( , . . . . .
. , PdCl2 , PdCl2 . . (+6), PtF6, . .
1. . .
2. . . . .
3. , ? .
4. (II): PtCI2×3NH3, PtCI2×NH3 KCI, PtCI2×2NH3. . .
5. , 44,8 (..).
6. , 6 (II) 30 .
7. +3? .
8. +4 +6.
9. : a)Os + KNO3 +KOH= b)K2RuO4 + CI2 = d) Pt +CI2 +HCI=.. e) Pt +H2O2 +KOH=.. h)RuO4 +H2SO4=.
10. : (IV) , (II) (II), (II)(II), , (IV)(II). .