1b ¡1 H Â/ñ · 2018-09-05 · C ¸+P8)C»Eý ¼-253eC A#è"X,º ... c8.7 /ñ Kd H Kd ï G ] ¸H...

Nankai University http://struchem.nankai.edu.cn Nankai University http://struchem.nankai.edu.cn

8.1

Nankai University http://struchem.nankai.edu.cn

8.2 8.2.1

6

6

6

2

_6

66


2 2 3 1 1 3

3 3 1 4 1


8.2.2

2

2

2

1


8.38.3.1 (A3)

1) ABABAB…

2) : 12( 6 3 )

hexagonal closest packing (hcp)


P (hP)3)

a = b = 2rc = 1.633ar

1

2

21,

31,

32;0,0,0


4)

:

4

243,

32,

31;

41,

32,

31

87,

31,

32;

81,

31,

32;

85,0,0;

83,0,0


1 41/4 1 8

(1331)2

61/6 1 6

(33)1

42

: : =2:2:4=1:1:2

A3


5) ~A3

001 a=2r=b, c/a=1.633

6) c

c c

3

100%

4 23= 74.05%sin(120 )

r

ab c

3 6hm


8.3.2 (A1)

1) ABCABC...

2) 12

3) cF

1

4

21,

21,0;

21,0,

21;0,

21,

21;0,0,0 cubic closest packing (ccp)


4)

: : =4:4:8=1:1:2

8 ( )

4 ( 1 3 )


5) 74.05%

36) 43

2 2a r

33

33


A1 A3

12: : =1:1:2

74.05%

A1 A3A1 4 A3A1

A1: Cu Ag Au Ni Pd Pt Al

A3: Mg Zn Nankai University http://struchem.nankai.edu.cn

8.4 8.4.1 (A2)

1) cI

2) : 8+6

body cubic packing (bcp)


a2

a

3) 68.02%

ar 344)

6 ( 3 3)

12( )


8.4.2 (A4)1) cF

2

4

2) 4

3) =34.01% 38ra

A4


A3 hcp A1 ccp A2 bcp A4ABAB... ABCABC...

12 12 8+6 4hP cF cI cF1 4 2 42 4 2 8

2 1 1 24 8 122 4 6

% 74.05 74.05 68.02 34.01


8.5

A3* La A5 -Sn A6 In A8 -Se

A9 A10 -Hg A11 -Ga A12 -Mn


A13 -Mn A14 I2 A15

A16 -S A17 P A20 U


• X•

•

12 8 6 4

1 0.97 0.96 0.88

1212


X A1a

100

ra 42 42ar

VNZM 0/ (Z M N0

V )


8.6 8.6.1

1)

Cu-Au

CuAu

Cu3Au


2) :

>2.0% <0.02%<0.25% >0.6%

8.6.2LaNi5 CaCu5

36

3 atmH0.083g cm-3

(0.089 10-3g cm-3) 1000-253 C

(0.07 g cm-3)Nankai University http://struchem.nankai.edu.cn

8.7

—

A3 A1 A2 A4—


8.8

NaCl CsCl ZnS

ZnS CaF2


NaCl •• 2(1 Cl-,1 Na+) • cF• 1 Cl-, 1 Na+

• 4• 6:6• A1 ccp• :• : 4/4=1• : 1, 3• : 1 3• (111) |AcBaCb|Cl-:

Na+: 21

210,

210

21,0

21

21,000

21

21

21,

2100,0

210,00

21

halite 5 3hO Fm m


CsCl •• 2(1 Cl-,1 Cs+) • cP• 1 Cl-, 1 Cs+

• 1• 8:8•• :• : 1/1=1• : 1• : 1Cl-: 000

Cs+: 21

21

21 1 3hO Pm m


ZnS •• 2(1 S=,1 Zn++)• cF• 1 S=,1 Zn++

• 4• 4:4• A1 ccp• :• : 4/8=1/2• : 8• : 4• (111) |AaBbCc|S=:

Zn++: 21

210,

210

21,0

21

21,000

43

41

43,

41

43

43,

43

43

41,

41

41

41

2 43dT F m sphalerite


ZnS •• 4(2 S=,2 Zn++)• P hP• 2 S=,2 Zn++

• 1• 4:4• A3 hcp• :• : 2/4=1/2• 4 ( 2, 2)

1 1• |AaBb|

S=:

Zn++: 21

31

32000

5 2 1 1 3 2 1 700 , 00 ,8 3 3 8 8 3 3 8

or 46 36vC P mc wurtzite


CaF2•• 3(2 F-, 1 Ca++)• cF• 2 F-,1 Ca++

• 4• 8:4•• :• : 4/8=1/2

81 ( )1 (8 1/8)( )3 (12 1/4) ( )3 (6 1/2) ( )

fluorite

5 3hO Fm m


4 Ca++:

8 F-: 43

41

43,

41

43

43,

43

43

41,

41

41

41

43

43

43,

41

43

41,

41

41

43,

43

41

41

21

210,

210

21,0

21

21,000

Na2O


•• 6(4 O=, 2 Ti4+)• tP• 4 O=, 2 Ti4+

• 1• 6:3•• :• : 2/4=1/2• :

1( ) 1( )2( )rutile

144 24hD P mnm


2 Ti4+:

4 O=:21

21

21,000

0uu21

21

21 uu

21

21

21 uuuu0,

u

u

u

u


A1 ccp

A2 bcp

A3 hcp

A4

NaCl

CaF2

ZnS

ZnS

TiO2

CsCl

NiAs


AB CsCl 2(1Cl-,1Cs+) cP 1 1Cl-,1Cs+ 0,0,0 1/2,1/2,1/2

NaCl( ) 2(1Cl-,1Na+) cF 4 1Cl-,1Na+ 0,0,0; 1/2,1/2,0;

0,1/2,1/2; 1/2,0,1/21/2,1/2,1/2; 1/2,0,0; 0,1/2,0; 0,0,1/2

ZnS( ) 4(2S=,2Zn++) hP 1 2S=,2Zn++ 0,0,0; 2/3,1/3,1/2 0,0,5/8; 2/3,1/3,1/8

ZnS( ) 2(1S=,1Zn++) cF 4 1S=,1Zn++ 0,0,0; 1/2,1/2,0;

1/2,0,1/2; 0,1/2,1/21/4,1/4,1/4; 3/4,3/4,1/4;3/4,1/4,3/4; 1/4,3/4,3/4

AB2 CaF2( ) 3(2F-,1Ca++) cF 4 2F-,1Ca++

1/4,1/4,1/4; 3/4,3/4,1/4;3/4,1/4,3/4; 1/4,3/4,3/4; 3/4,3/4,3/4; 3/4,1/4,1/4;1/4,3/4,1/4; 1/4,1/4,3/4

0,0,0; 1/2,1/2,0; 1/2,0,1/2;0,1/2,1/2

(TiO2)6(4O=,2Ti++) tP 1 4O=,2Ti++ 0,0,0; 1/2,1/2,1/2

1 1 1, ,0; , ,2 2 21 1 1, ,0; , ,2 2 2

u u u u

u u u u


CsCl 8 8 1/1=1 1NaCl( ) 6 6 A1 (ccp) 4/4=1 4 ,

1, 31 3

ZnS( ) 4 4 A3 (hcp) 2/4=1/2 4 ,

2, 211

ZnS( ) 4 4 A1 (ccp) 4/8=1/2 8

8

CaF2( ) 8 4 4/8=1/2

8 11 (8 1/8)

3 (12 1/4)3 (6 1/2)

13

(TiO2)6 3 2/4=1/2

4 11 (4 1/4)2 (4 1/2)

11


• —

• ,

• Lande( ) NaCl

8.9 1. (Goldschmidt)


NaCl

ra 42 ra 42a=2(r+ + r-)

a=2(r+ + r-)

(a) (c)(a)

(c)

+

+

+

+

+

+

+

+ +

+ +

+


MgO MnO CaO MgS MnS CaS

a/Å 4.21 4.44 4.80 5.19 5.21 5.68

CaMnMg rrrOSrr

MgS MnS MgS MnS(a)

Sra 42 ÅrS 84.14

20.52

NaCl ,


MnS CaSCaS (c)

2/68.584.1CaSCa rrr

ÅrCa 00.1

MgO MnO CaOMnO CaO (c)

280.400.1OOCarrr ÅrO 40.1

ÅrMn 82.0244.440.1MnOMn rrr

MgO (a)(b) 1.4142*4.21=5.95 1.40*4=5.60MgO (c)

71.0Mgr221.440.1MgOMg rrr


(Landé) 1920

1923 (Wasastjerna)

1926

F (1.33Å) O2 (1.32Å)80 ( )


*zC

zC

r nn Cnn

1927 Pauling

2. Pauling ( )

3. (Shannon )1969 Shannon Prewitt

(effective ionic radii)1976 Shannon —

— — —


1.

8.10

A

B C

D

r-

2r- + 2r+

rAB 2 )2(22)(2 rABrrAC

rrr 2 414.012rr


0.414 r+/r- <0.732 60.225 r+/r- < 0.414

4

2 3 4(ZnS)

6(NaCl)

8(CsCl, CaF2)

12

r+/r- 0.155 0.225 0.414 0.732 1


2. ( )

WW

CNCN

nn

n+:n- CN+ CN- W+:W-

CsCl 1:1 8 8 1:1NaCl 1:1 6 6 1:1

ZnS 1:1 4 4 2:2ZnS 1:1 4 4 2:2

CaF2 1:2 8 4 2:11:2 6 3 4:2


3.

AgF AgCl AgBr AgIrAg+ 1.13r 1.33 1.81 1.96 2.20

r+ + r 2.46 2.94 3.09 3.332.46 2.77 2.88 2.99

r+ / r 0.85 0.62 0.58 0.51CsCl NaCl NaCl NaClNaCl NaCl NaCl ZnS


AB

8 6 4 3 2CsCl NaCl ZnS


( )() (

)


8.11 Pauling

1928 Pauling:

—


12 9 8 81.0 0.732 0.732 0.645

7 6 40.592 0.414 0.225


— ( )

:S=W+/CN+

:CN

iiSW

1


Cl- 1

NaCl

Na+ : 6

Na+-Cl- :SNa+-Cl-=1/6

Cl- : 6

16616

1iiS

CN

iiSW

1

1


Ca2+ Ti4+

CaTiO3

Ti4+ 6

STi4+-O2-=4/6=2/3

Ca2+ 12

SCa2+-O2-=2/12=1/6

O2- Ti4+ :Ca2+ :

24 24

612

3242

1iiO SW

2


:(CN-)

( )( )

—


1 0.58 0.33

1 0.71 0.58


4.

5.

( )


8.12

8.12.1

SiC BN


-BN SiC


8.12.2

CdI2


8.12.3

: CO2 CO2P

4 CO2 P

I2

2 I24 I2


ZnS Zn S O1/3 H

1b ¡1 H Â/ñ · 2018-09-05 · C ¸+P8)C»Eý ¼-253eC A#è"X,º ... c8.7 /ñ Kd H Kd ï G ] ¸H...

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Transcript of 1b ¡1 H Â/ñ · 2018-09-05 · C ¸+P8)C»Eý ¼-253eC A#è"X,º ... c8.7 /ñ Kd H Kd ï G ] ¸H...