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第 14 章 卤 素 PowerPoint PPT Presentation


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第 14 章 卤 素. §14-1 卤素的通性. §14-2 卤素单质. §14-3 氟氯溴碘的化合物. Br 2. Cl 2. I 2. 卤 素 The Halogens. 拉丁文原义 ⅦA ns 2 np 5 “ 萤石” ← 9 F 2s 2 2p 5 “ 绿色” ← 17 Cl 3s 2 3p 5 “ 臭” ← 35 Br 4s 2 4p 5

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第 14 章 卤 素

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14

14-1

14-2

14-3


Br2

Cl2

I2

The Halogens

A ns2np5

9F 2s22p5

17Cl 3s23p5

35Br 4s24p5

53I 5s25p5

85At 6s26p5

21085 At 8.3



141 11


  • ns2np5

  • -10+1+3+5+7nd

  • F

  • F2

  • -1

  • -1NaClHCl[CuCl4]2-


F

[He]2s22p5

-1,0,

Cl

[Ne]3s23p5

-1,0,+1,+3,+4,+5,+7

Br

[Ar]4s24p5

-1,0,+1,+3,+4,+5,+7

I

[Kr]5s25p5

-1,0,+1,+3,+4,+5,+7

At

[Xe]6s26p5

-1,0,+1,+5


12

(CaF2)(Na3AlF6)(Ca5F(PO4)3)

.

I(NaIO3) 

NaClNaBr

At210At8.3

42He + 20983Bi 21185At + 2 10n


13



142 21

  • F2Cl2

  • p-p

  • I3-

  • Cl2Br2I2

  • F2Cl2Br2I2


(K)

(K)

(kJ/mol)

(X2/X-)(V)

F2

53.53

85.01

158

2.868

Cl2

172.17

239.18

242

1.358

Br2

265.9

331.93

193

1.0652

I2

386.7

457.50

151

0.535

At

575

610

110

0.2


22

(2).

FCo

2Co3F2 2CoF3

MgFeCuPbNiF

CoCl2 CoCl2

Cl2Fe

1


(2) .

2S(s)Cl2(g)S2Cl2(l)

S(s)Cl2(g)SCl2 (l)

2P3Cl22PCl3

2P5Cl2()2PCl5

Br2I2PPX3

2P3Br22PBr3()

2P3I22PI3H3PO3HI


3

X2 H2 2HX

C12 2Cl*Cl* + H2 HCl + H*H* + Cl2 HCl + Cl*


4

pH

4X2 + 2H2O 4HX + O2F2>Cl2>Br2

X2 + H2O HX + HXOCl2>Br2>I2

X2 +2e- 2X-X2/ XF2/ FCl2/ ClBr2/ BrI2/ I

(V):2.87 1.3583 1.085 0.535

O24H+4e-H2O1.229 V pH0

0.815V (pH7)

F2

2F22H2O4HFO2 G -209.2 kJ.mol-1

F2


X2H2O H+HXOX-

KcClBrI


4.

X22 OH- X-XO- H2O (XClBr) (1)

3I26OH- 5I-IO3- 3H2O

3X26OH- 5X-XO3- 3H2O (XClBrI) (2)

F

2F22OH-(2) 2F-OF2H2O

OF2O2

2F24OH- 4F-O22H2O


.Cl22e- = 2Cl-

.HClO = H+ClO-

.HClOH+ + e- = H2O1/2Cl2

.ClO-H2O + 2e- = 2OH-Cl-

.HClOH+ + 2e- = H2OCl-

pH>4Cl2

Cl2H2O H+HClOCl-PH<4Br2pH>6

BrO3-Br-I2pH>8


1986Karl Chrite F2

(1)4KMnO4+4KF+20HF4K2MnF6+10H2O+3O2

(2)SbCl5+5HFSbF5+5HCl

(3)2K2MnF6+4SbF5 4KSbF6+2MnF3+F2

23

KHF2

.

2F-F22e-

2HF-2+2e-H2+4F-

2KHF2 2KF+H2F2

LiFAlF3HF


F2

UF6235U

CCl3F

12CCl2F2

CBr2F2


.

2NaCl() 2Na(l) + Cl2(g)

2NaCl + 2H2O H2 + Cl2+ 2NaOH

2Cl-Cl2+2e-

2H2O+2e-H2+2OH-

MnO2,

,KMnO4

MnO2,

,KMnO4

MnO2 + 4HCl MnCl2 + Cl2 + 2H2O

2KMnO4 + 16HCl 2MnCl2 + 2KCl + 5Cl2 + 8H2O

MnO2 + 4HCl MnCl2 + Cl2 + 2H2O

2KMnO4 + 16HCl 2MnCl2 + 2KCl + 5Cl2 + 8H2O


. Cl2 + 2NaBr NaCl + Br2

2NaI + 3H2SO4 + MnO2 2NaHSO4 + I2 + 2H2O + MnSO4

I2NaIO3

2 IO3+5 HSO3-5 SO42-+I2+H2O+3H+

a.IO3+3 HSO3-3 SO42-+I-+3H+

b.I-IO3- IO3+5I-+6H+3I2+3H2O

U235


NaCO3

363K

PH=3.5

Br2

H2SO4

NaBr + NaBrO3

Br2

3Br2+3CO32- BrO3-+5Br+3CO2

BrO3-+5Br+6H+ 3Br2+3H2O

B: BrO3- +0.519 1/2 Br2 +1.065 Br

A: BrO3- +1.52 1/2 Br2 +1.065 Br


KIO3MnO2KCrO4

I2

MnO2 +2I- +4H+I2 +Mn2+ + 2H2O

IO3- + 5I- + 6H+ 3I2 + 3H2O


143 31

  • HFHI

  • 273K1500

  • HIHBrHClHF


(a). (b).

1400

HFHF(HF)2(HF)3359KHFHF


HFH2O H3O+F-Ka3.510-4

F-HFHF2-H2F3-H3F4-HF2-

HFF- HF2-K525

lmolL-1HF2-10F-l

H2F2H2O H3O+HF2-

H2F2

1 HFHClHBrHI

2 HIHBrHClHF

3 HI HBr lHC HF HF


4HF ()SiF4

SiO2+4HFSiF4+2H2O

CaSiO3+6HFCaF2+SiF4+3H2O

SiO2

HF

HFHF

5


HF,

HBrHI,,

1

H2Cl22HCl

2

HXH2SO4H3PO4

780K

CaF2+H2SO4CaSO4+2HF

NaCl+H2SO4NaHSO4+HCl

NaCl+NaHSO4Na2SO4+HCl

NaBr+H3PO4NaH2PO4+HBr

NaI+H3PO4NaH2PO4+HI


NaBr + H2SO4() NaHSO4 + HBr

NaI + H2SO4() NaHSO4 + HI

2HBr + H2SO4() SO2+ 2H2O + Br2

8HI + H2SO4() H2S+ 4H2O + 4I2


3

PBr3 + 3H2O H3PO3 + 3HBr

PI3 + 3H2O H3PO3 + 3HI

2P + 6H2O + 3Br2 2H3PO3 + 6HBr

2P + 6H2O + 3I22H3PO3 + 6HI


4.

C2H6(g) + Cl2(g) C2H5Cl(l) + HCl(g)

5.

HBrHI

Br2H2S2HBrS

I2H2SO3H2O2HIH2SO4


32

1

KF CaF2 MgF2

>673K

CaCl MgBr2 KI

FeCl2 CoCl2


2

HCl SF6 CCl4 PCl3

FeCl3 AlCl3 HgI2

a.P467

b.F-IP467



Cl2F2 2ClF3

ClF3(T)ClF5()BrF5()IF7()

IF3ClF5

1XXn/ n1357X X

BrClIClICl3IBr3

2


3

XXH2OHXOHX

3BrF35H2OHBrO3Br29HFO2

2ICl33H2OHIO3ICl5HCl HIO2

IF53H2OHIO35HF


KI I2 KI3

CsBrIBrCsIBr2

CsBr3 CsBrBr2

CsICl2 CsClICl


I2KII2I-I3-

I3- I2 I-

K=1.3510-3

KII3-

KI


33

(CN)2 (SCN)2 (OCN)2 (SeCN)2

927 1587 1587 1587

,

CN2SCN2OCN2SeCN2


2Fe + 3SCN2=2FeSCN3

2Fe+3Cl2=2FeCl3

HCN HSCN HOCN

4

3CN-+CuCN[Cu(CN)4]3-

2I-+HgI2[HgI4]2-

Fe2+ + 6CN- = [Fe(CN)6]4-


5

Fe2+Cl2O3CN-

Cl2+2KSCN2KCl+(SCN)2

Cl2+2KI2KCl+I2

MnO2+4HClCl2+MnCl2+2H2O

MnO2+4HSCN(SCN)2+Mn(SCN)2+2H2O

CN- + O3 OCN- + O2

2OCN- +3O3CO32-+ CO2+ N2+ 3O2

F- < OCN- < Cl- < Br - < CN- < SCN- < I- < SeCN-

Cl2+2OH- =Cl- + ClO- + H2O

(CN)2+2OH-CN-+CNO-+H2O


1(CN)2

(CN)2 :NCCN: d(C-N)113pm d(C-N)137pm

Cl2 (CN)2H2OHCNHCNO

2

CN-H+HCN

3 50mg

CN-H2OHCNOH-

AgCl2CN-[Ag(CN)2]-Cl-

4Au8NaCN2H2OO24Na[Au(CN)2]4NaOH


KCNSKSCN ()

2SCN-(SCN)22e-

Fe3+Fe3+

Fe3+nSCN- Fe(NCS)n(3-n)+n1,2,6

pH


OF2ClO2I2O5

34

OF2O2F2


O

O

Cl

OF2

OF2+2

OF2F22%NaOH

2F2+2NaOH2NaF+OF2+H2O

ClO2

2NaClO3+SO2+H2SO42NaHSO4+2ClO2

2ClO2+2OH-ClO3-+ClO2-+H2O

sp3


2HIO3 I2O5+H2O

I2O5CO

I2O5+5CO 5CO2+I2

I2O5



+1

HXO

+3

HXO2

+5

HXO3

+7

HXO4

.

XO-XO4-

1. Xsp3

2

.HXOHXO4

.HXOHXO4


HXOMXO

1.

HClO (2.9510-8) HBrO (2.0610-9)HIO (2.310-11)

XO- + H2O HXO + OH-

2.HOF-40F2HOFHFO2

X2H2O H+X-HXO X=ClBrI


KCl4.210-4 KBr7.210-9 KI210-13

HgOPbOAg2OCaCO3X-H+

2HgO + H2O + 2Cl2 HgOHgCl2 + 2HOCl

CaCO3 + H2O + 2Cl2 CaCl2 + CO2 + 2HOCl

Ag2OH2O Cl2 2AgCl2HClO


3.: HClO>HBrO>HIO

2HXO 2HX O2 (1)

3HXO 2HXHXO3 (2)

HBrBr2

4HBrO2Br2O22H2O

5HBrOHBrO32Br22H2O

(1)(1)(2)


B ClO3- 0.47ClO-0.81 Cl-

BrO3- 0.565BrO- 0.70 Br-

IO3- 0.145 IO- 0.49 I-

XO-C1O-348KC1O-CI-C1O3-348K

BrO-273K323353K

IO-

3I26OH-5I-IO3-3H2O


NaClNaClO

2Cl-2H2O Cl2 2OH-H2

Cl2 2OH- Cl- ClO-H2O

Cl-H2O ClO-H2

Cl2(298K)

2Cl22Ca(OH)2CaCl2Ca(ClO)22H2O

2Cl23Ca(OH)2CaCl2Ca(OH)2H2OCa(ClO)2H2O

Ca(ClO)2

35

HII2Cl2


HClO2

H2SO4Ba(C1O2)2BaSO42HClO2

8HClO26C1O2C124H2O

C1O2:

2ClO2 + 2OH- ClO2- + ClO3- + H2O

C1O2Na2O2NaC1O2

Na2O22C1O22NaClO2O2

3NaClO22NaClO3NaCl


HXO3MXO31

1

. HClO3HBrO3HIO3

40 50

8HClO33O23Cl24HClO42H2O

3HClO32ClO2HClO4H2O

4HBrO35O22Br22H2O

. HClO3HBrO3HIO3


.

BrO3-/Br2 ClO3-/Cl2 IO3-/I2

1.52 1.47 1.19

I2Br2Cl2Cl2Br2

2BrO3-2H+I22HIO3Br2

2ClO3-2H+I22HIO3Cl2

2BrO3-2H+Cl22HClO3Br2


2

Ba(XO3)2H2SO42HXO3BaSO4

Cl2HNO3H2O2O3

5Cl2I26H2O2HIO310HCl

HClAg2O

I210 HNO32HIO310NO24 H2O

Br25Cl26H2O2HBrO310HCl


2.

.ClBrI

.KClO3

2KClO3 2KCl3O2

629K668K

4KClO3 3KClO4KClO2

. >>

XO3- + 5X- + 6H+ 3X2 + 3H2O


2

.

3X26OH- 5X-XO3- 3H2O (XClBrI)

.

400K

NaClO3 + KCl KClO3 + NaCl

2NaCl+2H2O=====2NaOH+H2+Cl2

3Cl2 + 6OH-==== ClO3- + 5Cl- + 3H2O


(KClO3)

KClO3C12H22O11

()


HClO4 H5IO6 HIO4 HBrO4

55

HClO4

1. HClO4 KClO4+H2SO4()KHSO4+HClO4

KClO3H2O KClO4H2

HClO4365Kmp:161Kbp:363K

72HClO4


. HClO4

. ClO4- SO2H2SHIZnAlKClO4

. Cs+Rb+K+NH4+AgClO4

. MgBa

. KClO4KClO3

KClO4 KCl + 2O2

.NH4ClO4


2.

NaBrO3+F2+2NaOHNaBrO4+NaF+H2O

NaBrO3+XeF2+H2ONaBrO4+Xe+2HF

3.

Ba5(IO6)2 5H2SO4 5BaSO4 2H5IO6

Cl2 IO3- 6OH- IO6- 2Cl- 3H2O

HBrO4>H5IO6>HClO4


O

353K 373K 413K

2H5IO6H4I2O92HIO42HIO3+O2

-3H2O -H2O

Na3H2IO6Na5IO6

Mn2+MnO4-:

2Mn2++5H5IO62MnO4-+5IO3-+11H+ +7H2O


1.,

F2>Cl2>Br2>I2

HClO >HClO2 >HClO3 >HClO4

BrO3->ClO3->IO3-

HBrO4>H5IO6>HClO4


2. ,,;,

:

+1 +3 +5 +7

HClO HClO2 HClO3 HClO4

KClO KClO2 KClO3 KClO4


3.

HF,,,;;F2

4.

HF HCl HBr HI


END


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