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14

2325

14

, Si , Ge , Sn , Pb

Si

Ge

Sn

Pb

14

32

50

82

. .

2s22p2

3s23p2

3d104s24p2

4d105s25p2

4f145d106s26p2

()

77

117

122

140

152

I1 ()

11.26

8.15

7.90

7.34

7.42

I2 ()

24.38

16.35

15.93

14.63

15.03

I4 ()

64.49

45.14

45.71

40.73

42.32

Ae ()

1.26

1.38

1.2

1.2

2.6

1.9

2.0

1.8

1.9

AR

2.50

1.74

2.02

1.72

1.55

-4,0,(2),4

(-4),0,2,4

0,2,4

0,2,(4)

..

-4,0,2,4

Si

Ge

Sn

Pb

14

32

50

82

. .

2s22p2

3s23p2

3d104s24p2

4d105s25p2

4f145d106s26p2

()

77

117

122

140

152

I1 ()

11.26

8.15

7.90

7.34

7.42

I2 ()

16.35

15.93

45.14

45.71

11

14.63
I1, eV
40.73

15.03

I4 ()1,35

24.38
R,
64.49

Ae ()
1,20

1.26

1.38

1.2

10

1.2

--

1,05

2.6

1.9

2.0

1.8

1.9

AR

0,90

2.50

1.74

2.02

1.72

1.55

(-4),0,2,47

0,2,4

0,2,(4)

1,50

.. 0,75

-4,0,2,4
20

40

-4,0,(2),4
60

80

20

42.32

40

60

80

Si

Ge

Sn

Pb

14

32

50

82

. .

2s22p2

3s23p2

3d104s24p2

4d105s25p2

4f145d106s26p2

()

77

117

122

140

152

I1 ()

11.26

8.15

7.90

7.34

7.42

I2 ()

24.38

16.35

15.93

14.63

15.03

I4 ()

64.49

45.14

45.71

40.73

42.32

Ae ()

1.26

1.38

1.2

1.2

2.6

1.9

2.0

1.8

1.9

AR

2.50

1.74

2.02

1.72

1.55

-4,0,(2),4

(-4),0,2,4

0,2,4

0,2,(4)

..

-4,0,2,4

. .

2s22p2

2,6

Si

Ge

Sn

Pb

14

32

50

82

2,4

3s23p2

2,2

4d105s25p2

4f145d106s26p2

140

152

7.90

7.34

7.42

15.93

14.63

15.03

40.73
80

42.32

()

77

I1 ()

11.26

I2 ()

24.38

1,616.35

I4 ()

64.49

1,445.14

Ae ()

1.26

1.38

1.2

1.2

2.6

1.9

2.0

1.8

1.9

AR

2.50

1.74

2.02

1.72

1.55

-4,0,(2),4

(-4),0,2,4

0,2,4

0,2,(4)

..

-4,0,2,4

117

3d10P4s24p2

122

2,0

1,88.15

AR
20

45.71
40

60

.. ()

3300(.)

.. ()

G
/

Si

Ge

Sn

Pb

1420

945

232

327

3280

2850

2600

1740

,
,

() ..=14

(
)

CC
346

SiSi
236

GeGe
186

SnSn
151

C=C
598

Si=Si
310

Ge=Ge
270

Sn=Sn
190

1.12

0.66

0.09 ()

PbPb
92

CC
813
Eg ()

5.47 ()

.. ()

3300(.)

.. ()

G
/

Ge

Sn

Pb

1420

945

232

327

3280

2850

2600

1740

, T,
oC
3500
,
3000
,

2500

() ..=14

(
T, oC )

2000
CC
3461500

SiSi
236

GeGe
186

SnSn
151

1000
C=C
598 500

Si=Si
310

TGe=Ge
, oC
270

Sn=Sn
190

CC 0
813
Eg ()

Si

5.47 ()

20

1.12

40

60

0.66

80

PbPb
92

0.08 ()

.. ()

3300(.)

.. ()

G
/

Si

Ge

Sn

Pb

1420

945

232

327

3280

2850

2600

1740

,
,

() ..=14

(
)

CC
346

SiSi
236

GeGe
186

SnSn
151

C=C
598

Si=Si
310

Ge=Ge
270

Sn=Sn
190

1.12

0.66

0.08 ()

PbPb
92

CC
813
Eg ()

5.47 ()


600

500
3300(.)
.. ()
E=E
400
-.. ()
300

200
100

G
/

Ge Eg ()

Sn

Pb

1420

945
4

232

327

3280

2850
3

2600

1740

G
(/)Si

EE
,
20
40
60
80
,

1
0
20

() ..=14

(
40
60
80
)

CC
346

SiSi
236

GeGe
186

SnSn
151

C=C
598

Si=Si
310

Ge=Ge
270

Sn=Sn
190

1.12

0.66

0.08 ()

PbPb
92

CC
813
Eg ()

5.47 ()

sp3
d = 154

60

sp2

d(6,6) = 139

d = 142

d(5,6) = 146

-
,

2
F2

()

2
F2


1800

F2



10 , 10-15

+2


2010


1.
C () + 2 = 2

() + 2 = 2

() () .Go298 = 2.8 /
2.
to
12 () + 18HNO3 () C6(CO2H)6 + 18NO2 + 6H2O
3.
2C + F2
8C + K

HF
450 oC
180 oC

C + H2SO4 ()

2CF
KC8

HNO3

(sp2 sp3)
( )

()<0

[C24+][HSO4]2H2O

()>0

60
60Br24
[K(crypt-222)]260

H
O

2
20 , Na
0 o F
C

70

oC

60F60

O2

H
N
Li

F2,

l
IC H 6
C6

C6H6

60

350 oC

Br2 ()

F
M 2
D 22
K, yptr

K360

60F46 + C60F48

60H16 C60H36

60O

60Cl6

60
60Br24
[K(crypt-222)]260

H
O

2
20 , Na
0 o F
C

70

oC

60F60

O2

H
N
Li

F2,

l
IC H 6
C6

C6H6

60

350 oC

Br2 ()

F
M 2
D 22
K, yptr

K360

60F46 + C60F48

60H16 C60H36

60O

60Cl6


1. Si , C
Si + 2F2 = SiF4

..

Si + 2Cl2 = SiCl4

400 oC

Si + O2 = SiO2

600 oC

2. Si ,
Si + 2KOH + H2O

to

K2SiO3 + 2H2

3. Si F
3Si + 4HNO3 + 18HF = 3H2SiF6 + 4NO + 8H2O
4. Si Br2, I2, S, P, N, B
Si + 2P = SiP2

600 0C

Ge, Sn, Pb
1. , ,
Ge + 2Cl2 = GeCl4

(Sn)

+4

Pb + Br2 = PbBr2

+2

Pb + S = PbS

+2

Sn + S = SnS

+2

Sn + 2S = SnS2

+4

2. Ge, Sn
Sn + 2KOH + 4H2O = K2[Sn(OH)6] + 2H2
Ge + 2KOH + 2H2O2 = K2[Ge(OH)6]
3. Sn, Pb
Sn + 2HCl = 2SnCl2 + H2

(Pb ?)

Ge, Sn, Pb
4. Ge, Sn, Pb -
3Pb + 8HNO3 (30%) = 3PbII(NO3)2 + 2NO + 4H2O
Ge + 4HNO3 () = GeIVO2 + 4NO2 +2H2O
5. Ge, Sn, Pb NH3
2K + 5Pb + 2en

NH3 ()

[K(en)]2Pb5

Pb52
Sn52
Sn93
Ge93
Ge92

Ge94
Sn94

C, Si, Ge, Sn, Pb


1. ,
2. Si
SiO2 + 2C = 2CO + Si
SiO2 + 2Mg = 2MgO + Si
3. Ge Zn, Ni
GeO2 + 2H2 = Ge + 2H2O
4. Sn
SnO2 + C = Sn + CO2
5. Pb (PbS )
2PbS + 3O2 = 2PbO + 2SO2
PbO + CO = Pb + CO2

C, Si, Ge, Sn, Pb


:
: ,
: , , ,
,
: ,
: ,
:
Si: , ,
,
SiO2: , , , , ,

Ge: , -
Sn: , (, ),
,
SnO2: ,
Pb: ,

C, Si, Ge, Sn, Pb


1.

CH4, C2H6,

sp3

d = 154

E = 346 /

C2H4,

sp2

d = 135

E = 598 /

C2H2,

sp

d = 120

E = 813 /

Al4C3 + 12H2O = 3CH4 + 4Al(OH)3


CaC2 + 2H2O = C2H2 + Ca(OH)2
2.

Mg2Si + 4H2O = SiH4 + 2Mg(OH)2


SiCl4 + Li[AlH4]
SiH4

Et2O

500 oC, Ar

(. H+)

SiH4 + LiCl + AlCl3


Si + 2H2

SiH4 + O2 = SiO2 + 2H2O

SiH4

C, Si, Ge, Sn, Pb


3. GeH4, SnH4, PbH4
4.
CH4

SiH4

GeH4

.. ..

SnH4

PbH4

C, Si, Ge, Sn, Pb


-40

(oC)
3. GeH4, SnH4, PbH4-60

-80

-100
CH
4

4.

-120

SiH4

GeH4

SnH4

PbH4

-140

-160
SiH
GeH
SnH4
4
4

-180

CH4

PbH4

H4
SiH4 ..
GeH4 ..
SnH4
300
250
200
150

450

fHo298


400

350

E-H
/

300

100
50
0


250
200

-50
-100

150

H4

.. 100
..

SiH4 GeH4 SnH4 PbH4

H4

SiH4 GeH4 SnH4 PbH4


CF4

CCl4

CBr4

..,

-184

-23

94

..,

-128

77

187

d(C-X),

136

176

194

215

fGo298
/

-888

-61

67

260

200
150
100
50
0
-50
-100
-150
-200

200

()

CI4
171 ()

fGo298

-200

..

-400

..

-600
-800

CF4

CCl4

CBr4

CI4

CF4

CCl4

CBr4

CI4


CF4

CCl4

CBr4

-23 d(C-X), 94

CI4

..,

-184

..,

-128

77

187

d(C-X),

136

176

194

215

fGo298

-888

-61

67

260

2.0
1.5
1.0

200
150
100
50
0
-50
-100
-150
-200

1.5

0.5

2.0

171 ()

1.0
0.5

0.0
200

()
CF4

CCl4

CBr4

fGo298

0.0

/
CI4

-200

..

-400

..

-600
-800

CF4

CCl4

CBr4

CI4

CF4

CCl4

CBr4

CI4

SiC + 4F2 = SiF4 + CF4


CS2 + 2Cl2

FeS

( NaOH)

CCl4 + 2S

3CCl4 + 4AlBr3 = 3CBr4 + 4AlCl3


CCl4 + 4C2H5I

AlCl3

CI4 + 4C2H5Cl

:
1.
2.
3.


4. CCl4
La2O3 + 3CCl4 = 2LaCl3 + 3CO + 3Cl2

500 oC

5.
CCl4 + F2

to

CF2Cl2 + Cl2

-12

6. C2F4
CHCl3 + 2HF
2CHF2Cl

SbF5

700 oC

CF4

CHF2Cl + 2HCl

C2F4 + 2HCl

C2F4

Si, Ge, Sn, Pb


SiF4
.. 95

GeF4
.. 37

SnF4
.. 705

PbF4
.. 600

SiCl4
.. 68
.. 57

GeCl4
.. 50
.. 83

SnCl4
.. -36
.. 114

PbCl4
.. -15

SiBr4
.. 5
.. 153

GeBr4
.. 26
.. 187

SnBr4
.. 33
.. 203

SiI4
.. 122
.. 290

GeI4
.. 146
.. 377

SnI4
.. 146
.. 346

Si, Ge, Sn, Pb


SiF4
.. 95

GeF4
.. 37

SnF4
.. 705

PbF4
.. 600

SiCl4
.. 68
.. 57

GeCl4
800 T.., oC
.. 50

600.. 83

SnCl4
.. -36
F
.. 114

PbCl4
.. -15

SiBr4
.. 5
.. 153

400

GeBr4
.. 26
200.. 187

SnBr4
.. 33

.. 203
I

Br

Cl

GeI4
SnI4
SiI4
-200

.. 122
..
..
146
CX146
SiX4 GeX
4
4 SnX
4 PbX
4

.. 290
.. 377
.. 346

Si, Ge, Sn, Pb


1. 4 ( PbCl4)
Ge + 2Cl2

to

GeCl4

(NH4)2PbCl6 + H2SO4

0 oC

PbCl4+ (NH4)2SO4 + 2HCl

2. 4 ( SnF4, PbF4)

SnF4, PbF4
,
.. = 6

PbF4

3. 4 ( SiCl4, SiBr4, SiI4)


2KF + SiF4 = K2SiF6
2NaCl + SnCl4 = Na2SnCl6

Si, Ge, Sn, Pb


4. 4 ( SnF4, PbF4) ..
3SiF4 + 3H2O = H2SiO3 + 2H2SiF6
GeCl4 + 2H2O = GeO2 + 4HCl
SnI4 + H2O = SnOI2 + 2HI
5. PbCl4, GeI4, SnI4
SnI4

~ 380 oC

SnI2 + I2

6.
SnCl4 + 2HCl = H2SnCl6
GeBr4 + 2HBr = H2GeBr6
SnI4

H2SiF6
H2SiF6
pKa1 = -0.6

61%
d(SiF) = 169

SiF62

:
SiF62 PF61 SF6

3SiF4 + 3H2O = H2SiO3 + 2H2SiF6


SiO2 + 6HF (-) = H2SiF6 + 2H2O
SiF4 + 2NaF (-) = Na2SiF6

Ge, Sn, Pb
GeF2

GeCl2

GeBr2

.. 111

.. 143

SnF2

SnCl2

SnBr2

.. 210

.. 247
.. 623

.. 232
.. 660

PbF2

PbCl2

PbBr2

.. 500
.. 954

.. 373
.. 916

.. 818
.. 1292

GeI2
.. 240

SnI2
.. 320
.. 720

PbI2
.. 412
.. 900

Ge, Sn, Pb
1. 2 .. 6 (Ge) 9 (Pb)
2. SnX2, PbX2
Sn
Cl
O(H2O)

SnCl2

SnCl22H2O

3. SnX2 , PbX2 ( PbF2) ,


GeX2
GeCl2 + 2H2O = Ge(OH)2 + 2HCl

Ge, Sn, Pb
4. GeX2, SnX2, PbF2
SnBr4 + 2Sn

to, Ar

2SnBr2

5. PbX2 ( PbF2)
Pb(CH3COO)2 + 2KI = PbI2 + 2KCH3COO
6.

GeX2

SnX2

PbX2


SnCl2 + SO2 + 4HCl = H2[SnCl6] + S + 2H2O
7. SnCl3
8SnCl2 + Pt + 2PtCl2

to, Ar

Sn8Pt3Cl20


, 2, 32 (====)

..,

-205

..,

-191

-78

fHo298 /

-110.5

-393.5

fGo298 /

-137

-394

, /

1075

806

d(C-O),

113

116

, D

0.11

10 (N2, CN)

16 (N2O, N3)


, 2, 32 (====)

..,

-205

--

..,

-191

-78

fHo298 /

-110.5

-393.5

fGo298 /

-137

-394

, /

1075

806

d(C-O),

113

116

, D

0.11

10 (N2, CN)

16 (N2O, N3)


z*
*

s*
s
3 ()
2 ()

N2


1.
CO2 + C = 2CO
2. , ..
CO + NaOH

p, to, .

NaHCOO

()

3.
CO + 2H2
CO + H2O

to, .
to, .

CH3OH

CO2 + H2

Ni

4.
4CO + Ni = Ni(CO)4
H[CuCl2] + CO = Cu(CO)Cl + HCl

Ni(CO)4

-
.
CO + Cl2
COCl2
(, )

sp2
COCl2
COF2

COCl2

COBr2

..,

-114

-128

..,

-83

65

fGo298 /

-619

-205

-111

2
1.
+ 2 = 2

CO2

CaCO3 + 2HCl = CO2 + CaCl2 + H2O


2. ,
CO2 + H2O H2CO3
CO2 + 2NaOH = Na2CO3 + H2O
H2CO3 H+ + HCO3 2H+ + CO32
pKa1 = 3.9

pKa2 = 10.3

3.

CO32

2Fe + CO2 = 2FeO + C


4. : HCO3 , CO32
CO32 + H2O HCO3 + OH

CO2 () + 2 = 2aq + H2O

(1)

2aq + H2O = H2CO3aq

(2)

H2CO3aq = H+aq + HCO3aq

(3)

H+aq + HCO3aq = 2H+aq + CO32aq (4)

CO2 :

()

CO2

,
.


( ,
, , )

CaCO3:
,
,

Si, Ge, Sn, Pb


SiO

GeO

SnO

.. 1700

.. 770

SiO2

GeO2

SnO2

PbO2

.. 1728

.. 1116

.. 1360

.. 280
()

.. 1040

PbO
.. 886
()
()

Pb3O4 (2PbOPbO2)
-
Pb2O3 (PbOPbO2)
(), ()

2Pb3O4

550 oC

6PbO + O2

2Pb2O3

520 oC

4PbO + O2

Si, Ge, Sn, Pb


1.

SiO

GeO

SnO

PbO




2SiO = SiO2 + Si

( ..)

SnO + 2HCl = SnCl2 + H2O


SnO + 2KOH + 3H2O = K2[Sn(OH)4(H2O)2]
3GeO + 12HCl + 2BiCl3 = 2Bi + 3H2[GeCl6] + 3H2O
2.

SiO2

GeO2

SnO2

PbO2

SiO2
1. (Q), (T), ()
-Q

575oC

-Q

870oC

-T

163oC
-T

1470oC

-C

230oC
-C

120oC
-T
2.
-Q

1728oC

SiO2
3.

d(Si-O) = 160
E(Si-O) = 466 /

(/)

SiO2
4.
SiO2 + H2O
SiO2 + 2NaOH ()

SiO2 + 2F2 = SiF4 + O2


to

Na2SiO3 + H2O


5. H4SiO4
, pKa1 = 9.65
H2SiO3,
6. , Li+, Na+
Na2CO3 + 6SiO2 + CaCO3 = Na2CaSi6O14 + CO2
SiO44 + H2O HSiO43 + OH
H3SiO4

+ H2O H4SiO4 +

OH

2H3SiO41 H4Si2O72 + H2O

()


1.
Si2O76
2.

3. :
- 2 1[SiO3]2
LiAl(SiO3)2

Be3Al2Si6O18 ,

- 1[Si2O5]2


4.
3 2[Si2O5]2
Mg3(OH)2(Si2O5)2
5.
, Si Al Be

Na8(Al6Si6O24)S8
3

[AlnSi1-nO2]

Sn, Pb
1.

SnSO4 + 2H2O + 2NH3 = Sn(OH)2 + (NH4)2SO4


6Sn(OH)2 = Sn6O4(OH)4 + 4H2O

2.

Sn(OH)2 + 2NaOH = Na2[Sn(OH)4]

25 oC

2Sn(OH)2 + 2NaOH = Na2[Sn(OH)6] + Sn

100 oC

Na2[Sn(OH)6] + CO2 = SnO22H2O + Na2CO3 + H2O


Na2[Sn(OH)6] + 8HCl = H2[SnCl6] + 6H2O + 2NaCl

Sn6O4(OH)4

3.

3PbO2 Pb3O4 + O2

SnO
PbO

(~280 oC)

2PbO2 + 2H2SO4 = 2PbSO4 + O2 + 2H2O

C, Si, Ge, Sn, Pb


CS2

SiS2

.. 112

GeS2

.. 1100

SnS2

.. 840

.. 522

H2[SnCl6] + 2H2S = SnS2 + 6HCl


SnS2 + Na2S = Na2SnS3
SiS2 + H2O = H2SiO3 + H2S
GeS

.. 665

SnS

.. 881

PbS

.. 1077

SnCl2 + H2S = SnS + 2HCl


SnS + (NH4)2S2 = (NH4)2SnS3
Pb(CH3COO)2 + H2S = PbS + 2CH3COOH

HCN, HSCN
1. HCN, .. 13 , .. 26
pKa = 9.31
1000
CaC2 + N2
C + CaCN2 ()
CaCN2 + Na2CO3 + C = 2NaCN + CaCO3

HCN

NaCN + H2SO4 = HCN + NaHSO4


4NaCN + 5O2 + 2H2O = 4NaHCO3 + 2N2
4NaCN + 2CuSO4 = 2CuCN + 2Na2SO4 + C2N2

()

2. HSCN, .. 5 ,
()
HSCN HN=C=S; HSCN H+ + SCN
KCN + S

to

KSCN

pKa = 0.28

( Fe3+)

(CN)2

HCN, HSCN
1. HCN, .. 13 , .. 26
pKa = 9.31
1000
CaC2 + N2
C + CaCN2 ()
CaCN2 + Na2CO3 + C = 2NaCN + CaCO3
NaCN + H2SO4 = HCN + NaHSO4

HCN

4NaCN + 5O2 + 2H2O = 4NaHCO3 + 2N2

4NaCN
+ 2CuSO4 = CuCN + Na2SO4 + C2N2 ()

(CN)2

2. HSCN, .. 5 ,
()
HSCN HN=C=S; HSCN H+ + SCN
KCN + S

to

KSCN

pKa = 0.28

( Fe3+)


1. .
.
2. 9
.
3. .

(>>Si>Ge>Sn>Pb).
4.
, .
5. . Ge
Sn Pb ,
.
6.
. .. +2 ,
, .