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使用教材:许力等编著,《工程化学》,兰州大学出版社 授课对象:非化学类各专业学生 主讲教师:董文魁、许力、李静萍等 - PowerPoint PPT Presentation


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工程化学 —— 第五章 物质结构基础. 使用教材:许力等编著,《工程化学》,兰州大学出版社 授课对象:非化学类各专业学生 主讲教师:董文魁、许力、李静萍等. 第五章 物质结构基础. 第一节 氢原子结构. 一、人类对原子概念的认识. J.Dalton 的“原子论”. W.Thomson 的原子“浸入模型”. E.Rutherford 的原子“含核模型”. E.Schrodinger 的原子“波动模型”.

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4034284


4034284

J.Dalton

W.Thomson

E.Rutherford

E.Schrodinger


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Balmer n = 3,4,5,6

(1)


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2

  • 1913Bohr


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P P = mc

1924 L. de Broglie ( 1892 1987 )

L. de Broglie Einstein E = m c 2 E = h


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de Broglie P

P

1927 de Broglie

de Broglie


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Sohrodinger

1926 Sohrodinger )

E V m h


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n

1.

100 200210

nlm

1 n

1 2 3 4 n ( ) KLMN

n = 1 ( K )

n

E Z

eV 1 eV = 1.603 1019 J


4034284

n

H

n = 1 E = 13.6 eV n = 2 E = 3.40 eV

n E = 0 0

n 1234 n

2 l

n n

l 01234 ( n 1 ) n spdf g


4034284

n = 3 l 0 1 2

s p d

l n = 4

l 4 4

l = 0 s 4 s

l = 1 p 4 p

l = 2 d 4 d

l = 3 f 4 f

4 ( n ) 4


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3 m

m l l

m 0 1 2 3 l

2l + 1

l = 3 m = 0 1 2 3 7

m n l 2 p

n = 2 l = 1


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Ms

Ms = ms

4 ms

ms

m s + 1/2 1/2 Ms

n l m ms


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n= 4l = 3

l = 3 m = 0 1 2 3 7 7 + 1/2 1/2 2 7 = 14 n l m m s

n l m m s

4 3 0 1/2

4 3 1 1/2

4 3 1 1/2

4 3 2 1/2

4 3 2 1/2

4 3 3 1/2

4 3 3 1/2

n l m m s

4 3 0 1/2

4 3 1 1/2

4 3 1 1/2

4 3 2 1/2

4 3 2 1/2

4 3 3 1/2

4 3 3 1/2


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1 s

2s

2 p

1.


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W = V


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= | |2

w = | | 2 V

| | 2 | | 2


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| | 2

( r ) ( xyz )

3 1

2.


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z

s

+

x

z

px

+

x

z

pz

z

py

+

+

x

y


4034284

y

y

z

z

x

x

x

x

dxy

dx2y2

s

dz2

z

x

pz

1

2


4034284

y

z

z

dxy

dyz

dxz

+

+

+

x

y

x

+

+

+

z

y

+

+

+

x

x

+

d x2y2

d z2


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| R |2

1s

3s

2s

r

3.

r = R ( r ) Y ( ) r

R ( r ) r Y ( ) r

| |2 r | R |2 r

| R |2 r


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3 d

2p

3p

s r 0 | R |2 2s 1s 3 s

p r 0 | R |2 2p 3p 2

d r 0 | R |2 3d


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( ) n

n E 4 s = E 4 p = E 4 d = E 4 f

n E 1 s < E 2 s < E 3 s < E 4 s

n


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1.

Pauling

ns np

1s

2s 2p

3s 3p

4s 3d 4p

5s 4d 5p

6s 4f 5d 6p

7s 5f 6d 7p


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7 p

5f

6d

7s

6p

4f

5d

6s

5p

4d

5s

4p

3d

4s

3p

3s

p d f

2p

2s

1s


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Li

2

2.

1

+ 3

2

Z Z*


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Z* = Z

l

4s 4p 4d 4f

E 4 s < E 4 p < E 4 d < E 4 f

n l


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2

l

l

n l 3s 3p 3d

l


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1

2Pauli

3 Hund

d f p


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1 H Hydrogen 1s1

* 2 He Helium 1s2

7 NNitrogen 1s2 2s22p3

5 B Boron 1s2 2s22p1

9 FFluorine 1s2 2s22p5

8 OOxygen 1s2 2s22p4

10 NeNeon 1s2 2s22p6

3 Li Lithium 1s2 2s1

4 Be Beryllium 1s2 2s2

** 6 CCarbon 1s2 2s22p2


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11 Na Sodium 1s2 2s22p63s1

12 Mg Magnesium 1s2 2s22p63s2

13 Al Aluminium 1s2 2s22p63s23p1

14 Si Silicon 1s2 2s22p63s23p2

15 P Phosphorus 1s2 2s22p63s23p3

16 Si Sulfur 1s2 2s22p63s23p4

17 Cl Chlorine 1s2 2s22p63s23p5

18 Ar Argon 1s2 2s22p63s23p6


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* 19 K Potassium [Ar] 4s1

20 Ca Calcium [Ar] 4s2

** 21 Sc Scandium [Ar] 3d14s2

22 Ti Titanium [Ar] 3d24s2

23 V Vanadium [Ar] 3d34s2

24Cr Chromium [Ar] 3d54s1

25 Mn Manganese [Ar] 3d54s2

26 Fe Iron [Ar]3d64s2

27 Co Cobalt [Ar]3d74s2

28 Ni Nickel [Ar]3d84s2

* [ Ar ] Ar 1s2 2s2 2p6 3s2 3p6

** 4s 3d 3d 4s


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1.

2.


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1

H

He

2

Li

Be

B

C

N

O

F

Ne

1.

2

2 1 1s 1

8

8 2 2s 2p 4


4034284

3

Na

Mg

Al

Si

P

S

Cl

Ar

4

K

Ca

Sc

Ti

V

Cr

Mn

Fe

Co

Ni

Cu

Zn

Ga

Ge

As

Se

Br

Kr

5

Rb

Sr

Y

Zr

Nb

Mo

Tc

Ru

Rh

Pd

Ag

Cd

In

Sn

Sb

Te

I

Xe

8

8 2 3s 3p 4

18

18 3 4s 3d 4p 9

18

18 3 5s 4d 5p 9


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Tl

Pb

Bi

Po

At

Rn

6p

5d

Hf

Ta

W

Re

Os

Ir

Pt

Au

Hg

4f

Ce

Pr

Nd

Pm

Sm

Eu

Gd

Tb

Dy

Ho

Er

Tm

Yb

Lu

6s

Cs

Ba

La

7p

6d

Ac

Rf

Db

Sg

Bh

Hs

Mt

Uun

Uuu

Uub

Th

Pa

U

Np

Pu

Am

Cm

Bk

Cf

Es

Fm

Md

No

Lr

5f

Fr

Ra

7s

32

32 4 6s 4f 5d 6p 16

32

32 4 7s 5f 6d 7p 16


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s IA IIA n s 1 ~ 2

p IIIA IVA VA VIA

VIIA 0 VIIIA ns 2 np 1 ~ 6

s p s p 8 0 VIII A


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d III B IV B V B VI B

VII B VIII ( n1 ) d 1 ~ 8 ns 2 ( n1 ) d 456

d ( n1 ) d ns 8 VIII

ds ( n1 ) d 10 ns 1 ~ 2

d ds

ds ns

f ( n2 ) f 0 ~ 14 ( n1 ) d 0 ~ 2 ns 2 ( n2 ) f f III B


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d

d r=

2.

(2)


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Na

r = 154 pm r= 188pm

r>r

( HeNe )


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(a)

Z r

r

d5d10f7f14 r


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Na

Mg

Al

Si

P

S

Cl

Ar

4

Sc

Ti

V

Cr

Mn

Fe

Co

Ni

Cu

Zn

3

r/pm 154 136 118 117 110 104 99 154

Na Cl7 r 55 pm 10 pm

Ar

r/pm 144 132 122 118 117 117 116 115 117 125

Sc Ni8 r 29 pm 4 pm


4034284

Sc

Ti

V

Cr

Mn

Fe

Co

Ni

Cu

Zn

r/pm 144 132 122 118 117 117 116 115 117 125

CuZn d10 r

10 pm 4 pm

Z* r

Z* r


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Li 123 pm

Na 154 pm

K 203 pm

Rb 216 pm

Cs 235 pm

r

(b)

Z r

r


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Ti V Cr

r/pm 132 122 118

Zr Nb Mo

145 134 130

Hf Ta W

144 134 130

r

1213 pm

r


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r/pm 169 165 164 164 163 162 185 162

Tb

Dy

Ho

Er

Tm

Yb

Lu

r/pm 161 160 158 158 158 170 158

La

Ce

Pr

Nd

Pm

Sm

Eu

Gd

Eu 4f7 6s2f Yb 4f14 6s2f

15 r 11 pm (n2) f Z* r

15 11 pm


4034284

15

K Ca Sc Ti V Cr

r/pm 203 174 144 132 122 118

Rb Sr Y Zr Nb Mo

r/pm 216 191 162 145 134 130

Cs Ba La Hf Ta W

r/pm 235 198 169 144 134 130


4034284

(2)

1 mol 1 1 mol (M+ ) ( I1 )

1 mol (M+ ) 1 mol 1 mol (M2+ ) I2

M ( g ) M+ ( g ) + e H = I1

M+( g ) M2+ ( g ) + e H = I2

I3 I4 In

1 mol kJmol1


4034284

1 mol 1mol (M ) E1 E2 E3 E4

F ( g ) + e = F ( g ) H = 322 kJmol 1

E1 = H = 322 kJmol 1

E H

Z r

E


4034284

B C N O F

E / kJmol1 23 122 ( 58 ) 141 322

E ( 58 )

E

kJmol1

F 322

Cl 348.7

Br 324.5

I 295

N [ He ] 2s2 2p3 2p N E

F F E

O S Se


4034284

F Cl F2 Cl2 ?

F2 Cl2

1/2 F2 ( g ) F ( g ) H1 = 154.8 kJmol 1

1/2 Cl2 ( g ) Cl ( g ) H2 = 239.7 kJmol1

F ( g ) + e F ( g ) H3 = 322 kJmol1

Cl ( g ) + e Cl ( g ) H4 = 348.7 kJmol1

1/2 F2 ( g ) F ( g ) F ( g )

H5 = H1 +H3


4034284

I

E

H5 = 154.8 + ( 322 ) = 167.2 kJmol

1/2 Cl2 ( g ) Cl ( g ) Cl ( g )

H6 = H2 +H4

= 239.7 + ( 348.7 ) = 109 kJmol

  • H5 < H6

    F2 Cl2


4034284

Li Be B C N O F

X 0.98 1.57 2.04 2.15 3.04 3.44 3.98

Cl 3.16 Br 2.96 I 2.66

1932Pauling

4.0


4034284
F

1916 Kossel ( )

1.

( NaCl )

Na e Na+ Cl + e Cl

2s 2 2p 6 3s 1 2s 2 2p 6 3s 2 3p 5 3s 2 3p 6

Ne Ar


4034284

V F

0

Vr0

r0

r

r

V

r

Na+ Cl V

r > r0 r

V


4034284

F

q1 q2

r ,F

1

2


2 1 2 2 8 3 18 4 18 2 5 8 18
2. F1 22 83 18418+25 8 18


4034284

F

1 ( Valence Bond Theory )

1927Heitler London H2

Lewis

a

b


4034284

E F

0

D

ro

R

1

1s

r V

H2

H

1s 2 H

r = r 0 V

E= D ( D > 0 D < 0 )

H


4034284

F2


4034284

3 Fpz

1s

+

+

z

z

+

+

HCl


4034284

+ F

+

z

z

pz

pz

+

+

Cl 3pz H 1s z

Cl 2


4034284

+ F

+

z

z

pz

pz

+

+

Cl 3pz H 1s z

Cl 2


4034284

+ F

+

+

+

3

HCl 3p 1s

Cl 2 3p 3p


4034284

x F

x

px

+

+

z

180

+

+

  • 180

    px z

YOZ


4034284

N F2

px py pz

z pz pz px px py py

N2 3 1 2


4034284

F4

:298.15K1mol


4034284

F

2p

2p

2s

2s

CH4 C

4

4 4 H CH4

AlCl 3 120 NH4+ 10928


4034284

FPauling 1931


4034284

CH4 2s 2px2py2pz 4 sp3 sp3 s p


4034284

+

+

Be sp

2s 2 2p0

1.sp

+

+

=

sp s p 1/2

180

BeCl2

2 sp 2 Cl 3p


4034284

BCl 3

B sp2

2. sp2

3 sp2 3 Cl 3p BCl 3


4034284

CH 4C sp3 4

4 H 1s

CH4

3. sp3


4034284

sp3 H 1s

sp3 H2O V

HOH 10928

10445

O

H

H

4.

C sp3 4 sp3

H2O V O sp3


4034284

1.

HCl q d = q d


4034284

H2O

H2O

BCl3

BCl 3

D

HI HBr HCl NH3 H2O

/ D 0.38 0.79 1.03 1.66 1.85 1.15



4034284


4034284

1.0 10 2 kJ mol1 kJ mol1

1

2


4034284

kJmol1

Ar 0 0 8.49

HCl 3.305 1.104 16.82


4034284

a )

b )

c )

d ) F 1 / r7

e )

HeNeArKrXe b. p. m. p. b. p.

3

F 2


4034284

1

HF F r

F H H r F H F H

1 r ( FO N ) H

2 r ( FON )


4034284

2

a

H 1 H

H H

b

H

F H F O H O N H N

E / kJ mol1 28.0 18.8 5.4

c

H


4034284

CH3CH2OH

H3COCH3

HNO3

3

b. p.

HF HCl HBr HI

b. p. HCl < HBr < HI HF HF b. p. b. p. H2ONH3b. p.


4034284

m. p. 44 45

H2O HF ( H2O ) 2 ( H2O ) 3 ( HF ) 2 ( HF ) 3 ( H2O ) 2 4 ( H2O ) 2 4

m.p. 113 114


4034284

NaCl NaCl

NaCl 58.5


4034284


4034284

1

r r Hg 2 + Pb 2 + Ag +

Si 4 + < Al 3 + < Mg 2 + < Na+ < ( Ne ) < F < O 2

Na+ < Cu+ Ca 2 + < Cd 2 +

2

SO4 2 ClO4 NO3 r

IS2Ag+Hg2 +Pb2 +

Be 2 +Al 3 +Si 4 +SO4 2


4034284

r Na + > K + > Rb + > Cs +

Li + H

r

Mg 2 + ( 8e65 pm ) < Ti 4 + ( 8e68 pm )

r

Pb 2 +Zn 2 + ( 1818 + 2 ) >

> Fe 2 +Ni 2 + ( 8 ~ 18 ) >

> Ca 2 +Mg 2 + ( 8 e )


4034284


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