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12

1
2
3

Ru
+

Rh

Os

Ir

Pd

Pt


Ru

Rh

Pd

Os

Ir

Pt

. N

44

45

46

76

77

78

.
.

4d75s1

4d85s1

4d105s0

5d66s2

5d76s2

5d96s1

134

134

137

135

136

139

I1 ()

7.37

7.46

8.34

8.7

9.1

9.0

I2 ()

16.76

18.01

18.43

17.0

17.0

18.6

AR

1.42

1.45

1.35

1.52

1.55

1.44

..

(2),3,4,6,8 (1),2,3,4,(6)

2,4

(3),4,6,8 (1),2,3,4,5,(6)

2,4,(6)


Ru

Rh

Pd

Os

..,

2607

..,

2237

1828

3306

2719

2100

4173

3730

3413

5300

4405

4200

aH0,
/

642.7

556.9

378.2

791.0

665.3

565.3

,/(107)

1.41

2.33

1.02

1.23

2.13

1.04

d, /3

12.37

12.41

12.02

22.59

22.56

21.45

Mg

Cu

Cu

Mg

Cu

E0(M3+/M0),

+0.61

+0.76

+0.85

+1.0

E0(M2+/M0),

+0.8

+0.92

Ir

E0(M3+/M0), E0(M2+/M0) > 0

Pt

Cu

+0.98


1.
Os + 2O2 = OsO4 (200 )

Ru + O2 = RuO2

(400 oC)

2Rh + 3O2 = 2Rh2O3


Ir + O2 = IrO2
2Pd + O2 (1 ) = 2PdO

,
T

Pt + O2
2.
Ru + 3F2 = RuF6
2Rh + 5F2 = 2RhF5
Pd + 2F2 = PdF4

Os + 3F2 = OsF6

Pt + 3F2 = PtF6

2Ir + 5F2 = 2IrF5


3. > 1000 oC S, Se, Te, P, Si, C, B,
N2
Pd + S = PdS

Ir + 3P = IrP3

Ru + Si = RuSi

4.
5.
Ru + 3NaNO3 + 2NaOH () = Na2RuVIO4 + 3NaNO2 + H2O
Os
Ir + 2NaNO3 + 2NaOH () = Na2IrIVO3 + 2NaNO2 + 2H2O
Rh
2Rh + 3BaO2 = Rh2IIIO3 + 3BaO
Ir


6. -
Pd + 4HNO3 () = Pd(NO3)2 + 2NO2 + 2H2O
Pd2+
3Pt + 4HNO3 + 18HCl = 3H2[PtCl6] + 4NO + 8H2O
Pt4+
Ru, Rh, Os, Ir + HNO3 + HCl
Pt + 2HNO3 + 4HCl + Cl2 = H2[PtCl6] + 2NO2 + 2H2O
Rh, Ir
7. 2,


1.
2. (.% 106)
Ru 10

Rh 2

Pd 8

Os 2

Ir

Pt 10

3.
Pt (80%), Rh+Ir (5%), Pd (1%), Os (0.5%), Au (0.5%),
Ru (0.1%) + Fe, Mn + Ni, Cu
4.
15-40% Ir + 50-80% Os + Al, Fe, Co, Ni, Mn
5. Pd Ni, Cu
6. Ru: RuAs2 , Ni

Ir


1.

Pt, Rh, Ir , ,

2.

Pt, Pd, Rh

3.

Pd

4.

Pt

5.

Ru, Ir

6.

Pd

7.

Ir, Ru, Os ,

RuCl33H2O
Pt, Rh, Ir

8.

.. Ru, Os
1.
Os + 2O2 = OsO4

Na2RuO4 + Cl2 = RuO4 + 2NaCl

OsO4

2. Os(VIII)
OsO4 + 2KOH = K2[OsO4(OH)2]

OsO4 + 2NaF = Na2[OsO4F2]


OsO4 + F2 = Os2O3F2 + O2
OsO4 + NH3 + KOH = K[OsO3N]
3.

[F(OsO2F3)2]+

2OsVIIIO4 + C2H5OH + 5KOH = 2K2[OsVIO2(OH)4] + CH3COOK


2RuVIIIO4 + 4KOH = 2K2RuVIO4 + O2 + 2H2O
3K2RuO4 + HNO3 = 2KRuO4 + RuO2 + 4KNO3 + 2H2O
Ru6+ Ru7+ + Ru4+

Ru, Os (IV)
1. : RuF4, RuCl4, OsF4, OsCl4, OsBr4
t2g4eg0, = 2.8

Ru + 2Cl2 + 2KCl = K2[RuCl6]


OsCl4 + 2KCl = K2[OsCl6]

K2[OsCl6] + en = [OsCl4(en)] + 2KCl

RuO4 + 14HCl + 4KCl = K4[Ru2OCl10] + 7H2O + 4Cl2


-
2. RuO2, OsO2

RuO2 : -, .. = 1200
OsO2 : -, .. = 600

RuO2

Ru + O2 = RuO2 (400 oC)


OsO4 + H2 = OsO2 + 2H2O (25 oC)
3.
RuO2 + SrCO3 = SrRuO3 (700

oC)

[Ru2OCl10]4

2K4[Ru2OCl10] + 6H2SO4 + 16H2O = [Ru4O6(H2O)12](SO4)2 +


4K2SO4 + 20HCl

.. Ru, Os
1. : MX3 ( OsF3), MX2 ( MF2)
2Ru + Cl2 = 2RuCl3

2RuO4 + 16HI (aq) = 2RuI3 + 5I2 + 8H2O

2RuO4 + 16HCl () + 6KCl = 2K3[RuCl6] + 5Cl2 + 8H2O


2. Ru, Os (III)

RuCl33H2O + 2NaCl = Na2[RuCl5(H2O)] + 2H2O


RuCl33H2O + 3H2C2O4 = H3[Ru(C2O4)3]+3HCl+3H2O -
2K2[OsO2(OH)4] + 16HCl () + 2KCl = 2K3[OsCl6] + 12H2O + 3Cl2
[Ru(H2O)6]3+ + e = [Ru(H2O)6]2+

E0 = +0.23

[Ru(NH3)6]3+ + e = [Ru(NH3)6]2+

E0 = +0.24

3. Ru(II)
[Ru(NH3)5(H2O)]Cl2 + N2

[Ru(NH3)5(N2)]Cl2 + H2O

.. Rh, Ir
1. Rh, Ir (VI,V)
RhF6, IrF6, RhF5, IrF5
RhF6 = RhF5 + F2
5IrF6 + Ir = 6IrF5

IrF5

120 oC
350 oC

2IrF6 + H2O = 2IrO22H2O + O2 + 12HF


RhF6 + 3Cl2 = 2RhF6 + 6ClF

2. Rh, Ir (IV)
RhF4, IrF4, IrO2 ( Ir)
IrO2 + 4HCl + 2KCl = K2[IrCl6] + 2H2O -
(NH4)2[IrCl6] + 2H2 = Ir + 2NH3 + 6HCl
K2[IrCl6] + 2KI = K3[IrCl6] + I2
Rh(IV)

IrF4

Rh, Ir (III)

1. .. Rh, Ir
3 Rh2O3
2. Rh(III)
[RhIVF6]2

[Rh(NH3)6]Cl3

q)
(a
3

N
H

00
(1

BF3

H3
N

[RhCl(NH3)5]Cl2

[RhH(NH3)5]2+

Zn
NH3

Rh2O3nH2O

HC l
OH

RhCl33H2O
H+
OH
[RhCl6]3

OH

Rh2O3nH2O

[Rh(H2O)6]3+
HC l o
,t
O
H2

Rh, Ir (III)
3. Ir(III)

[IrIVCl6]2

[Ir(NH3)6]Cl3

K3[IrCl6]
[IrCl6

]3

C
)

0
(1
0

N
H

)
C

KCl

50
(1

HCl

H3
N

HNO3

[IrCl(NH3)5]Cl2

IrCl33H2O

H2O, to
HCl ()

[Ir(H2O)6

]3+

CH3CN

OH
O2

[Ir(CH3CN)3Cl3]

IrO2nH2O

4. ,
E

eg

t2g

= 12/5 O

Rh3+, Ir3+ (d6)

.. Rh, Ir
1.
RhCl33H2O
RhCl33H2O
K3[IrCl6]

CH3COOH
CH3OH, to
PPh3
C2H5OH, to

CO, PPh3
to, p

[Rh2(CH3COO)4]2H2O

Rh24+

[RhCl(PPh3)2] Rh1+

[IrCl(CO)(PPh3)2]

Ir1+

2. Rh(II) Rh24+
3. Rh(I), Ir(I) , d8
d8 d6
[IrCl(CO)(PPh3)2] + I2 = [IrCl(I)2(CO)(PPh3)2]
4.
2RhCl33H2O + 6CO = Rh2(CO)4Cl2 + 2COCl2 + 6H2O
K3[IrCl6]

CO, CH3OH

Ir4(CO)12

Rh2(CO)4Cl2

Pd, Pt (IV)
1. .. Pd, Pt +2, +4.
PtF6 -
PtF6 + O2 = O2[PtF6]

Pt5+

2. PdO2, PtO2
PtCl4 + 4KOH + (n2)H2O = PtO2nH2O + 4KCl
(n=2)
K2[PtCl6] + 2Na2CO3 = PtO2 + 4NaCl + 2KCl + 2CO2

PtO22H2O + 2NaOH = Na2[Pt(OH)6]


PtO22H2O + 6HCl () = H2[PtCl6] + 4H2O

Pd, Pt (IV)
2.
PdF4, PtX4
Pt + 2Cl2 = PtCl4 (300 oC) -
PtCl4 + 5H2O = [PtCl4(H2O)2]3H2O
[PtCl4(H2O)2]3H2O + 2HCl = H2[PtCl6] + 5H2O
(NH4)2[PtCl6] + 6NH3 () = [Pt(NH3)6]Cl4 + 2NH4Cl
H2[PtCl6] + KCl = K2[PtCl6] + HCl
H2[PtCl6] + 4KI = PtI4 + 2HCl + 4KCl
H2[PdCl6] + 2NaI = H2[PdCl4] + I2 + 2NaCl
PtCl4

PtI4

Pd, Pt (II)
1. .
2, PtF2
Pd + Cl2 = PdCl2 (500 oC)

.. = 680

PtCl4 = PtCl2 + Cl2 (400 oC)

.. = 580

:
PdCl2 + 2HCl = H2[PdCl4]
H2[PtCl6] + SO2 + 2H2O = H2[PtCl4] + H2SO4 + 2HCl
:
PdCl2 + CO + H2O = Pd + CO2 + 2HCl
-PdCl2

Pd, Pt (II)
2.
PdO .. = 900 , PtO .. = 350
PdCl2 + 4NaNO3

600 oC

PdO + Na2O + 2NaCl + 2N2 + 5O2

PdCl2 + 2KOH = Pd(OH)2 + 2KCl

Pd(OH)2 + 2HClO4 + 2H2O = Pd(ClO4)24H2O


[Pd(H2O)4]2+
Pd(OH)2 + 2KOH = K2[Pd(OH)4]

H2[PtCl4] + 4KOH = PtO2H2O + 4KCl + H2O

PdO

Pd, Pt (II)
1.
E

dx2-y2

[Pd(NH3)4]2+, [Pt(NH3)4]2+,
dxy

[PdCl4]2, [PtCl4]2

dz2

=0

dxz dyz

[Pt(NH3)4]2+

[Pt(NH3)4]Cl2 + K2[PtCl4] = [Pt(NH3)4][PtCl4] + 2KCl


]2

[PtCl4

+ H2O [PtCl3(H2

O)]

pK = 1.87

[PtCl3(C2H4)]

2.
K2[PtCl4] + C2H4 SnCl2 K[PtCl3(C2H4)] + KCl

H2[PtCl4] + 5SnCl2 + 3KCl = K3[Pt(SnCl3)5] + 2HCl

[Pt(SnCl3)5]3

Pd, Pt (II)
3.
(, 1926): CN > NO > PR3 > NO2 >
I > SCN > Br > Cl > I > F > OH > NH3 > py > H2O

-
H2[PtCl4] + 2NH3 = cis-[PtCl2(NH3)2] + 2HCl
[Pt(NH3)4]Cl2 + 2HCl = trans-[PtCl2(NH3)2] + 2NH4Cl
Cl

NH3

Pt
Cl
NH3

NH3

Pt

NH3

NH3

NH3

Cl

Cl

Cl

Cl

NH3

Cl

NH3

Cl

NH3

HCl
NH3

HCl

Pt
NH3

NH3

trans

Pt
NH3

cis
[PtCl2(NH3)2]

Pt

Cl

Pt
NH3

Cl

Cl

Cl

Pd, Pt (II, IV)


1. - PtCl3, PtBr3, PtI3, Pt3I8
2H2[PtCl4] + Cl2
2PtI4

to

to

2PtCl3 + 4HCl

2PtI3 + I2

Pt2+[PtI6]2

PtCl3

2. -
K2[PtCl6] + K2[PtCl4] +KCl = K5[Pt2Cl11]
[PtBr2(NH3)2] + [PtBr4(NH3)2] = 2PtBr3(NH3)2
3.
K2[Pt(CN)4] + 0.15Br2 () = K2[Pt(CN)4]Br0.3
-

[Pt2Cl11]5

Pt2.3+

, d(PtPt) = 289


1. Pd Pd(NO3)2
2. Pt, Rh, Ir ,
Rh + HNO3 + 4HCl + Cl2 = H3[RhCl6] + NO2 + H2O
Ir + 2HNO3 + 4HCl + Cl2 = H2[IrCl6] + 2NO2 + 2H2O {+Pt}
3. (NH4)2[PtCl6]
4. (NH4)3[RhCl6]
5. Ru, Os; RuO2
6.
Pd(NO3)2 = Pd + 2NO2 + O2

(200 oC)

(NH4)2[PtCl6] = Pt + Cl2 + 2HCl + 2NH3

(600 oC)

(NH4)2[IrCl6] + 2H2 = Ir + 2NH3 + 6HCl

(400 oC)

(NH4)3[RhCl6] KOH

o
2Rh2O3 1000 C 4Rh + 3O2

OsO4 + 4H2 = Os + 4H2O

RuO2 + 2H2 = Ru + 2H2O