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第 21 章. P 区元素. Chapter 21 p -Block Elements. 本章教学要求. 1.掌握 Al 、 Sn 、 Pb 单质及其化合物的性质,了解其用途;. 2.了解锗分族、锑和铋单质及其化合物的性质及变化规律;. 3。了解铝的冶炼原理及方法。. 21 .1 p 区金属概述 21 .2 铝 镓分族 21 .3 锗分族 21 .4 锑和铋 21 .5 钋(自学) 21 .6 p 区金属6 s 2 电子的稳定性. 本章内容. IIIA. p 区金属元素 在周期表中的位置.

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P 区元素

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P

21

P

Chapter 21 p-Block Elements


P

1AlSnPb

2

3


P

21.1 p

21.2

21.3

21.4

21.5

21.6 p6s2


P

IIIA

p


21 1 p

pAlGaInTlGeSnPbSbBiPoPo

ppAlGaInGeSnPbTlPbBi.

pns2np1-4 nsnp2

pp

21.1 p


P

P


P


P

(Aluminum).

1.5107 .

2.31010 .

2 Al2O3 4 Al + 3 O2

() ()

Al2O3NA3AlF6(2-8%)

10%CaF21233-1253K,

4.5-7.0V

21.2

21.2.1

1


P

Al2O3.2H2O

Na2CO3

NaOH

Al(OH)3

Al2O3

Al2O3

CO2


P

  • O2 S N2 P C .

    2 Al(s) + (3/2) O2(g) = Al2O3(s), = - 1676 kJ mol-1

    .

2 (Al2O3) [Al(OH)3]

a-Al2O3g -Al2O3

.

(Cr3+)(Fe3+,Cr3+)/(Fe3+)


P

AlF3 AlCl3 AlBr3 AlI3

.

AlCl3 + 3 H2O Al(OH)3 + 3HCl

Al2Cl6

AlCl3

2Al+ 3Cl2 (g) 2AlCl3

2Al+ 6HCl (g) 2AlCl3 + 3H2 (g)

Al2O3 + 3C + 3Cl2 2AlCl3 + 3CO

AlCl3

3

(1) ()

(2)

  • (Al3+ +3HCO3-=Al(OH)3+3CO2)KAl(SO4)2.12H2O.


P

Be

B

C

Li

Si

AI

Na

Mg

21.2.2

. 2 3 (diagonal rule).

2 LiBeB 3 3 MgAlSi 3.

. . .


P

Li+Mg2+


P

Be2C + 4 H2O 2 Be(OH)2 + CH4

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


P

H3BO3 H2SiO3

BBSiSi

HBF4 H2SiF6


P

80%,

P,IIIV,GaAs

25%289K

,,

InPbInSn

21.2.3


P

:Tl-Ag,,

TlHg(8.7%)20K

Tl+Ag+TlOHCO2TlXAgX(X)TlClAgClTlBrTlITl2S

Tl


P

21. 3

21. 3. 1

  • SnO2

    (PbS)


P

21. 3. 2

  • (11.35g/cm3)

  • +IV+II

    +4Ge>Sn>Pb

    +2Ge<Sn<<Pb

  • GeSnGePbPb(II)

1


P

2

  • Pb21-5

    Pb+X2==PbX2

    Sn+X2==SnX4(SnX2)

    Ge+X2==GeX4

    Pb+S==PbS

    Sn+S==SnS2(SnS)

    Ge+S==GeS2


P

Sn+2HCl() = SnCl2+H2

HCl Pb+2HCl PbCl2+H2 ()

Pb+4HCl() = H2[PbCl4] +H2

Ge+4H2SO4() = Ge(SO4)2 +2SO2+ 4H2O

(GeO2 H2O)

H2SO4 Sn+4H2SO4() = Sn(SO4)2 +2SO2+4H2O

Pb+H2SO4() = PbSO4 + H2()

Pb+3H2SO4() = Pb(HSO4)2 +SO2+2H2O

Ge+4HNO3() = GeO2 H2O+4NO2+2H2O

Sn+4HNO3() = H2SnO3+4NO2+H2O

HNO3 4Sn()+10HNO3() = 4Sn(NO3)2+NH4NO3+3H2O

3Pb+8HNO3() = 3Pb(NO3)2+2NO+4H2O

Pb(NO3)2,Pb


P

Ge+4H2SO4() = Ge(SO4)2+2SO2+4H2O

(GeO2 H2O)

Ge+4HNO3() = GeO2 H2O+4NO2+2H2O

(2)SnSn(II)

(1)Ge

Sn+2HCl()===SnCl2+H2

4Sn()+10HNO3()===4Sn(NO3)2+NH4NO3+3H2O

Sn+4H2SO4()===Sn(SO4)2+2SO2+4H2O

Sn+4HNO3()=== H2SnO3+4NO2+H2O

(3)GeSnGe(IV)Sn(IV)

Pb+2HClPbCl2+H2()

Pb+4HCl()===H2[PbCl4]+H2

Pb+H2SO4() ===PbSO4 +H2()

Pb+3H2SO4()===Pb(HSO4)2+SO2+2H2O

3Pb+8HNO3()===3Pb(NO3)2+2NO+4H2O HNO3PbHNO3

(4)PbPb(II)


P

1

21. 3. 3

  • MO2MOMO2MOMO


P

1SnO2

SnO2+2NaOH==Na2SnO3+H2O

SnO2+2Na2CO3+4SNa2SnS3+Na2SO4+2CO2

SnO2n

H2COCH4SnO2SnO2


P

2PbO()PbO2,Pb3O4(,2PbOPbO2)

: PbOPb(II)


P

PbO2+NaOH===Na2PbO3+H2O

PbO2+4HCl====PbCl4(PbCl2Cl2)+H2O

PbO2+4HCl====PbCl2+Cl2+H2O

2Mn(NO3)2+5PbO2+6HNO3=2HMnO4+5Pb(NO3)2+2H2O

PbO2+H2SO4()===PbSO4+O2+H2O

PbO2---Pb3O4+O2----PbO+O2

: Pb3O4()Pb2II[PbIVO4]

Pb3O4 +HNO3=== PbO2+ Pb(NO3)2+H2O


P

Question

Pb3O4

Pb3O4 HNO3

Pb3O4 + 4 HNO3 == 2 Pb(NO3)2 + PbO2 + 2 H2O

Pb2+ PbO

Mn2+

2 Mn2+ + PbO2 + 4 H3O+ == 2 MnO4- + 5 Pb2+ + 6 H2O

PbO2

Pb3O4 2 PbO PbO2


P

2

21-7


P

GeSnPbMX4MX2(CSiMX4)

GeSnPb

GeSnPbHXX-

MX4GeCl4SnCl4SnCl4


P

SnCl2

2HgCl2 + SnCl2 == Hg2Cl2 + SnCl4

()

Hg2Cl2 + SnCl2 == 2Hg+ SnCl4

()

Hg2+ Sn2+

[Sn(OH)4]2- Bi(OH)3

2 Bi(OH)3 + 3 [Sn(OH)4]2- == 2 Bi + 3 [Sn(OH)6]2-

Bi3+.

Pb() . Pb(NO3)2 Pb(Ac)2 Pb() .

PbCl2 + 2HCl == H2[PbCl4] PbI2 + 2I- == [PbI4]2-


P

3

Sn4+Sn2+

4


P

21.4.

  • VA

  • +III+V+III+V+V


P

(Sb2S3)(Bi2S3)

21.4.1


P

,,

,

2Sb+6H2SO4()Sb2(SO4)3+SO2+6H2O

2Bi+6H2SO4()===Bi2(SO4)3+SO2+6H2O

  • .


P

1

MH3SbH3 BiH3228K

2

+IIISb4O6 Sb2O3+VSb4O10 Bi2O5

Sb2O3: ,,

21.4.2


P

(g/100g)

2.04

(298K)

0.002

(288K)

/K

588

()

548

()

929

109.3

/K

738

1698

kJmol-1

914.62

696.64

576.97

As4O6

Sb4O6

Bi2O3

As3+

(SbO)2SO4

(BiO)2SO4

Bi(NO3)3


P

+III+VBi(v)Mn2+MnO4-


P

3

  • SbF5SbCl5BiF5

As

Sb

Bi


P

MX3

X

F

Cl

Br

I

*

/K

*

/K

*

/K

*

/K

AsX3

267

256.8

304

413

SbX3

565

346

370

444

BiX3

9981003

506.5

492

681

*


P

  • MCl3+2H2O = M(OH)2Cl+2HCl

    MOCl


P

4.

M3+MO33-MO43-H2S

Bi2S5 Bi(V)

M S 2-

3Na2S + M2S3 == 2Na3MS3 (M=As, Sb), Bi2S3

3Na2S + M2S5 == 2Na3MS4 M=As, Sb)


P

21.6. P6S2()

(1)

Tl, Pb Bi ( PbO2, NaBiO3 ) ( Bi2S5, PbS2, PbBr4, PbI4 ). Ga, Ge, As Ga(), Ge(), As() ( AsO33-).


P

(2)

p 3.

Ga () Ge () As ()Se ()

In () Sn () Sb ()Te ()

Tl () Pb () Bi ()Po ()

Ga () Ge () As () Se ( )

In () Sn () Sb () Te ()

Tl () Pb () Bi () Po ( )


P

Question

N () Bi () +5 . .

p , , . , +3 . , .


P

671014


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