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第 15 章. 氮 族 元 素. 主 要 内 容. 氮的单质. 1. 氮的成键特征. 2. 3. 氮的氢化物. 主 要 内 容. 氮的含氧化合物. 4. 磷及其化合物. 5. 6. 砷、锑、铋. 氮 族元素包括氮、磷、砷、锑、铋 5 元素,在周期表中处于 VA 族。. 氮 绝大部分以单质形式存在于 大气 中 , 动植物体内的 蛋白质都 含氮 ,自然 界最大的硝酸盐矿是 智利 的 硝石 矿。. 磷在自然界以磷酸盐的形式存在,如 磷酸钙矿 ,磷灰石矿及 其 他 磷酸盐矿物 。.

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第 15 章

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15


1

2

3


4

5

6


5 VA


As4S4 As2S3 Sb2S3 Bi2S3


151

N2

1511 N2

N2 N

1 2


N2 + 3 H2 2 NH3

N2 + O2 2 NO

1512 N2

N2

O2


410

3 Mg + N2 Mg3N2

N2 Mg Ca SrBa

N2 Sr 380 Ba

260 Li 250

6 Li + N2 2 Li3N


1513 N2

N2

N2 N2

O2

P2O5 H2O


N2

NH4Cl + NaNO2

NaCl+ 2 H2O + N2


8 NH3 + 3 Br2 6 NH4Br + N2

NH4 2Cr2O7 s

Cr2O3 + 4 H2O + N2

2 NH3 + 3 CuO 3 H2O + N2+ 3 Cu

N2


152

1521

N

LiCaMg

N3 N3


1522

N

NH3NCl3N2H4 N sp3

N


P

2


NH3 N2H4 [Co NH34]2+[Pt NH3 2 N2H42]2+

N2 [Os NH35 N2 ]2+ [ NH3 5Ru N2 Ru NH35]4+

1523


153

1531

1

3 H2 + N22 NH3


3 H2 + N2 2 NH3


2 NH4Cl + Ca OH 2

CaCl2 +2 H2O + 2 NH3

Mg3N2 + 6 H2O

3 Mg OH 2 + 2 NH3

NH3


2

N sp3 3

NH


PH3


2 NH3 NH4+ + NH2

K 1.9 1033


Na + n NH3 Na+ + e n

NH3

e NH3n

NH3


NH3 Na

2 Na + 2 NH3

2 Na+ + 2 NH2 + H2

H2 NaNH2


AgCl + 2 NH3 [Ag NH3 2]+ + Cl

1

AgCl


F

H

H

B +

F

N

H

N

H

F

H

H

F

B

F

F

BF3


NH3 + H2SO4 NH4 2 SO4

NH3 NH3 H2O,

NH3 H2O ;

NH3 H2O NH4+ + OH

Ka 1.8 105


3 Mg + 2 NH3 Mg3N2 + 3 H2

NH3 H , H2N HN

2

2 Na + 2 NH3 2 NaNH2 + H2

NH4Cl + 3 Cl2 4 HCl + NCl3


3

2 NH3 NH4+ + NH2


4 NH3 + COCl2

CO NH22 + 2 NH4Cl


4 NH3 + SOCl2

SO NH2 2 + 2NH4Cl


2 NH3 + HgCl2

Hg NH2 Cl+ NH4Cl


Pt

4 NH3 + 5 O2 4 NO + 6 H2O

4

NH3 N 3

4 NH3 + 3 O2 2 N2 + 6 H2O


NH3

2 NH3 + 3 Br2 N2 + 6 HBr

CuO

2 NH3 + 3 CuO

N2 + 3 Cu + 3 H2O


NH4NO3 N2O + 2 H2O

NH4NO2 N2+ 2 H2O

NH4 2Cr2O7

N2+ 2 H2O + Cr2O3

NH3


3

NH4Cl NH4Ac


NH4 3PO4 3 NH3 + H3PO4

NH4 2SO4 NH3 + NH4HSO4

( )

NH4HCO3 NH3 + CO2 + H2O

H+


4


CO NH2 2 + ClO+ OH

N2H4 + Cl + H2O + CO32

1532

N2H4 NH3 H NH2

NaClO N2H4

2 NH3 + ClO N2H4 + Cl + H2O

NaClO


N2H4 , NN


= 1.75

D

1.4

113.6


N2H4 N2 + 2 H2

Ni

3 N2H4 N2 + 4 NH3


N2H4 + H2O N2H5+ + OH

K1 8.7 107

NH3

HClH2SO4

N2H5Cl N2H4 HCl

N2H6SO4 N2H4 H2SO4


Co3+ + 6 N2H4 [ Co N2H4 6 ]3+

Pt2+ + 2 NH3 + 2 N2H4

[ Pt NH3 2 N2H4 2]2+

N2H4 N


N2H4 N 2

N2H5+ / NH4+E = + 1.28 V

N2 / N2H5+E= 0.23 V


N2H4 + 4 AgBr

N2 + 4 Ag + 4 HBr

N2H4 + 2 X2 N2 + 4 HX


N2H4 + O2 N2 + 2 H2O

NO2H2O2 N2

2 N2H4 + 2 NO2 4 H2O + 3 N2

N2H4 + 2 H2O2 4 H2O + 3 N2


1533

hi

NH2OH NH3 H OH

NH2OH N

NH2OH N 1


NH3OH2SO4NH2OH 2 H2SO4

NH2OH + H2O NH3OH+ + OH

Kb = 8.7 109

N2H4 + H2O N2H5+ + OH

K1 = 1.3 106

HClH2SO4

NH3OHCl NH2OH HCl


N2 N2O

2 NH2OH + 2 AgBr

2 Ag + N2 + 2 HBr + 2 H2O

2 NH2OH + 4 AgBr

4 Ag + N2O+ 4 HBr + H2O


1534

HN3

N2H4 + HNO2 HN3 +2H2O

NaN3 HN3

NaNH2 + NaNO3

NaN3 + NH3 +3 NaOH


3 2 1

N N 1 H


N 1N 2N 3

3

4

N 1 sp2 N 2 sp


HN3

HN3 H+ + N3

Ka 2.4 105

N3 AgN3


Pb N32 2 Pb + 3 N2

PbIIAgI


154

1541

1 N2O

N2O

NH4NO3 N2O + 2 H2O


N2O

N2O N3


N2O

N2O N2O

N2O

N2O


3 Cu + 8 HNO3

3 Cu NO3 2 + 2 NO + 4 H2O

2 NO

NO

NO

NO


NO

N

NO


NO

NO

NO2

NO NO+NOClNOClO4

NO


3 N2O3

NO NO2 N2O3

NO + NO2 N2O3

N2O3 HNO2 273 K N2O3

N2O3


N , NN 186 pm, NN 147 pm

N2O3 N2O3

N2O3 NO + NO2


2 Pb NO32

2 PbO + 4 NO2+O2

4 NO2N2O4

NO O2 NO2 NO2

NO2 N2O4

2 NO2 N2O4


N pz 1 pz

3

4

N2O4 + 4 NO2


NO2

NO2 NO HNO3

3 NO2 + H2O 2 HNO3 + NO

NO3+ NO2

2 NO2 + 2 OH

NO3+ NO2+ H2O


5 N2O5

HNO3 NO2 N2O5

6 HNO3 + P2O5 3 N2O5 + 2 H3PO4

2 NO2 + O2 2 N2O5 + O2

N2O5


N pz4

O 1 pz

3

4

N2O5


N2O5

[NO2+][NO3]

NO2 O2

N2O5


1542

1

:

H+ + NO2 HNO2

NO NO2

HNO2

NO2 + NO + H2O 2 HNO2


Pb + NaNO3 PbO + NaNO2

2 NaNO3 O2+ 2 NaNO2


2

,


NO2 V

3

4


3

HAc

HNO2 H+ + NO2

Ka 7.2 104

2 HNO2 + 2 I+ 2 H+

2 NO + I2 + 2 H2O


5 NO2 + 2 MnO4+ 6 H+

5 NO3 + 2 Mn2+ + 3 H2O

HNO2+ HNO3 NO2+ H2O

HNO2 HNO3 HNO2


HNO2 H+ HNO2 +3 HNO2 H+

HNO2 + H+ NO+ + H2O


0 oC

2 HNO2 N2O3 + H2O

N2O3 NO2+ NO

3 HNO2 HNO3 + 2 NO + H2O


IA IIA

AgNO2 140 oC

2 AgNO2 NO + Ag

AgNO2


K3[Co NO26 ]

Co2++7 NO2+ 3 K+ + 2 H+

NO + K3[Co NO26] + H2O

NO2 N


Pt

4 NH3 + 5 O2 4 NO + 6 H2O

1543

1

1

2 NO + O2 2 NO2

3 NO2 + H2O 2 HNO3 + NO


2

NaNO3 + H2SO4

NaHSO4 + HNO3


HNO3 N sp2 N p O p

3

4

2


NO3

4

6


3

4 HNO3 4 NO2+ 2 H2O + O2


AuPtRh Ir


Cu + 4 HNO3

Cu NO32 + 2 NO2+2 H2O

NO2

NO

S + 2 HNO3 H2SO4 + 2 NO


6 Hg + 8 HNO3

3 Hg2 NO3 2 + 2 NO + 4 H2O

HNO3 NO

HNO3

NO2NON2O N2 NH4+


4 Zn + 10 HNO3

4 Zn NO3 2 + N2O+ 5 H2O

4 Zn + 10 HNO3

4 Zn NO3 2 + NH4NO3 + 2 H2O


MnS + 2 HNO3

Mn NO3 2 + H2S

Zn + 2 HNO3

Zn NO3 2 + H2

HNO3


HNO3 FeAlCr


4

1:3

Au + HNO3 + 4 HCl

HAuCl4 + NO + 2 H2O

3 Pt + 4 HNO3 + 18 HCl

3 H2PtCl6 + 4 NO + 8 H2O


Au3+ + 3 e Au

E 1.50 V

NO3+ 4 H+ + 3 e

NO + 2 H2O

E 0.96 V


Cl

[AuCl4]Au3+/ Au

AuCl4 + 3 e Au + 4 Cl

E 1.00 V


AuPt


5


2 NaNO3 2 NaNO2 + O2


2 Pb NO3 2

2 PbO + 4 NO2 + O2

MgCu Mg Cu


100 oC

300 oC

Hg2 NO3 2 2 HgO + 2 NO2

2 HgO 2 Hg + O2

2 AgNO3 2 Ag + 2 NO2 + O2


>300 oC

NH4NO3 N2O + 2 H2O

100 oC

>300 oC

2 NH4NO3

2 N2+ 2 O2+ 2 H2O

Mn NO3 2 MnO2 + 2 NO2


Mg NO3 2 6 H2O

Mg OH NO3 + HNO3 + 5 H2O


Cu OH NO3 CuO + HNO3

4 HNO3 4 NO2 + O2 + 2 H2O

Cu NO3 2 6 H2O

Cu OH NO3 + HNO3 + 5 H2O

CuO NO2


6

NO2 NO2


Fe NO 2+


7

H2N2O2

H2N2O3

HOONO

HNO4


155

1551

1

3 P3 Na3P

P3


2

3 3 PCl3

sp3d 5 PCl5

3 H3PO4P sp3 3


d dp

3s2 3p3 sp3

sp3


3 OH

1

sp3


p 1 p

p 3d


d p dp

dp


3

PH3

3d PCl5

d Cl PCl6


Ca3 PO4 2 + 6 SiO2 +10 C

CaSiO3 + P4 + 10 CO

1552

1


= 0 , = 0

f H

m

f G

m

2

P4


P44 4

PPP = 60


P4 P4O6 P4

O2



3

P4 + 6 H2O PH3 +3 H3PO4


4 P + 3 NaOH + 6 H2O

PH3+3 NaH2PO2

PCl3 PCl5


P4O6 P4O10

2 P + 5 CuSO4 + 8 H2O

5 Cu + 2 H3PO4 + 5 H2SO4


Cu P Cu3P

11 P + 15 CuSO4 + 24 H2O

5 Cu3P + 6 H3PO4 + 15 H2SO4


Ca3P2 + 6H2O 3Ca OH 2 + 2PH3

1553

1


PH4I+ NaOH NaI + H2O + PH3

P4S+ 3OH+ 3H2O

3H2PO2 + 2PH3


2

PH3 NH3 PH3

PH3 NH3


PH3 PH4X

PH4X PH4+

H+ PH4+


PH3 NH3

PH3 P3d d d


P H+ d PH3 H+

PH3

8 CuSO4 + PH3 + 4 H2O

H3PO4 + 4 H2SO4 + 4 Cu2SO4


Cu2SO4 PH3

PH3 CuI

4 Cu2SO4 + PH3 + 4 H2O

H3PO4 + 4 H2SO4 + 8 Cu

PH3 CuI

3 Cu2SO4 + 2 PH3

3 H2SO4 + 2 Cu3P


PH3 H3PO4

423 K

PH3 + 2 O2 H3PO4

PH3


1554

1

P4 P P O2

P O P4O6


+ 3 O2

P4O6

P4O6


P4O6 H3PO3

P4 O6 + 6 H2O 4 H3PO3

H3PO4

P4O6 + 6 H2O

PH3 + 3 H3PO4


2

P4O6 P O P4O10

P2O5


P4O10

P4O10

P4O10 PV

P4O10


HPO3 n > H4P2O7 > H3PO2 > H3PO3 > H3PO4

1555

sp3


1

H2PO2

P4 + 3 NaOH + 3 H2O

PH3 + 3 NaH2PO2


H3PO2 OH

H3PO2 H+ + H2PO2

K= 5.9 102


H3PO2

H3PO2

H2PO2 + 2 Ni2+ + 6 OH

2 Ni + PO4 3 + 4 H2O


2

P4O6 + 6 H2O 4 H3PO3

PCl3 + 3 H2O H3PO3 + 3 HCl

H3PO3 74.4


H3PO3

K1 = 3.7 102K2 = 2.09 107


4 H3PO3 3 H3PO4 + PH3

H3PO3


P4O6 + 6 H2O 4 H3PO4

HNO3

3

+5

P4O10 HNO3


Ca3 PO4 2 +3 H2SO4

3 CaSO4 + 2 H3PO4

1


K1 = 7.1 103, K2 = 6.3 108, K3 = 4.8 1013


FePO4 + PO43 Fe PO4 23

FePO4

Fe3+ + PO43 FePO4

H3PO4

:


n H3PO4 n H2O + HPO3 n

H3PO4

2 H3PO4 H2O + H4P2O7

3 H3PO4 2 H2O + H5P3O10


n H3PO4 nH2O + HPO3 n

n H3PO4 n1 H2O +

n+2

n

3n+1

HPO

2

H3PO4


H2O + H4P2O7 2 H3PO4


3


> >


PO43 + 12 MoO42 + 24 H+ + 3 NH4+

NH4 3PMo12O406H2O+6H2O

PO43


PO43 + Mg2+ + NH4+

MgNH4PO4



PnO

3n+1

3 3

PO3

n

n

n

n+2


170 oC

2 NaH2PO4 H2O + Na2H2P2O7

625 oC

n Na2H2P2O7 n H2O + NaPO3 2n

2 Na2HPO4 H2O + Na4P2O7

2 Na2HPO4 +NaH2PO4

2 H2O + Na5P3O10



1556

1

P sp3


PCl3 + 3 C2H5OH

P C2H5O 3 + 3 HCl

PCl3 + 3 H2O H3PO3 + 3 HCl


P sp3d

PF5 > PCl5 > PBr5


PF5

PCl5 PBr5

PCl5 PCl4+PCl6

PBr5 PBr4+ Br


PCl5 + 4 H2O H3PO4 + 5 HCl

PCl5 + H2O POCl3 + 2 HCl


2

P S P4S3P4S5P4S7P4S10

P4 S PPP


3 +1 +3 +5

PH3H3PO2H3PO3H3PO4

P4S3

P4S10


156


1561


+3 H3AsO3 Sb NO33

+5 H3AsO4 H[Sb OH 6]

+3 Bi NO33


HSb OH 6

Bi + 4 HNO3

Bi NO3 3 + NO + 2 H2O

3

+ 5


1562

MH3


Na3As + 3 H2O 3 NaOH + AsH3

As2O3 + 12 HCl + 6 Zn

6 ZnCl2 + AsH3+ 3H2O

AsH3 AsH3


AsH3

2 AsH3 2 As + 3 H2

Marsh


As


0.007 mg As

NaClO NaClO

2 As + 5 ClO + 6 OH

2AsO43 + 5 Cl + 3H2O


SbO33 + 9 H+ + 3 Zn

3 Zn2+ + SbH3+ 3H2O

SbH3

2 SbH3 2 Sb + 3 H2


BiH3 45 oC

AsH3SbH3 BiH3

2 AsH3 + 3 O2

2 As2O3 + 3 H2O


Gutzeit 0.005 mg As

AsH3

2 AsH3 + 12 AgNO3 + 3 H2O

As2O3 + 12 HNO3 + 12 Ag


1563

M2O3 M2O5

1 + 3

As2O3 Sb2O3 Bi2O3


As2O3

As2O3 3 mol dm3


As2O3

H3AsO3

AsCl4

As2O3


H3AsO3 Sb OH 3

Sb2O3

Bi2O3 Bi3+ BiO+

+3


Bi V

+3

+3

NaH2AsO3 + 4 NaOH + I2

Na3AsO4 + 2 NaI + 3 H2O


2 + 5

+5

As2O5

H3AsO4


Sb V HSbOH 6

Sb 6

Bi2O3 Bi V


Bi OH 3 + Cl2 + 3 NaOH

NaBiO3+ 2 NaCl + 3 H2O

Bi V NaBiO3

AsVSb VBi V


HI I2

H3AsO4 + 2HI H3AsO3 + I2 + H2O

BiO3 Mn2+ MnO4

5 BiO3+ 2 Mn2+ + 14 H+

5 Bi3+ + 2 MnO4+ 7 H2O


1564

PCl3 > AsCl3 > SbCl3 > BiCl3

AsCl3 PCl3

AsCl3 + 3 H2O H3AsO3 + 3 HCl


SbCl3 BiCl3 , SbOCl BiOCl

SbCl3 + H2O SbOCl + 2 HCl

BiCl3 + H2O BiOCl +2 HCl

SbCl3 BiCl3


AsF5SbF5BiF5

AsCl550 oC SbCl5 140

oC


As2S3As2S5 Sb2S5 Sb2S3 Na2SNH42S NaOH

1565

As2S3 As2S5 Sb2S3 Sb2S5

Bi2S3


Sb2S5 + 3NH4S 2NH4SbS4

2

3

As2S3 + 6 NaOH

Na3AsS3 + Na3AsO3 + 3 H2O

Sb2S3 + 6 NaOH

Na3SbS3 + Na3SbO3 + 3 H2O

As2S3 + 3 Na2S 2 Na3AsS3

Sb2S3 + 3 Na2S 2 Na3SbS3


As2S3 Sb2S3 Na2S NH42S2

As2S3 + 2NH4S2

As2S5 + 2NH4S

2

2

Sb2S3 + 2 NH4S2

Sb2S5 + 2NH4S

2

2


As2S3 As2S5 Sb2S3

Bi2S3 4 mol dm3

Sb2S3 + 12 HCl

2H3SbCl6 + 3 H2S

Bi2S3 + 6 HCl 2 BiCl3 + 3 H2S


2NH4SbS4 + 6 HCl

6 NH4Cl + Sb2S5 + 3 H2S

3

2 Na3AsS3 + 6 HCl

6 NaCl + As2S3+ 3 H2S

The end


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