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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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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

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J.Dalton

W.Thomson

E.Rutherford

E.Schrodinger


Balmer n = 3,4,5,6

(1)


2

  • 1913Bohr


P P = mc

1924 L. de Broglie ( 1892 1987 )

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


de Broglie P

P

1927 de Broglie

de Broglie



Sohrodinger

1926 Sohrodinger )

E V m h


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


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


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


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


Ms

Ms = ms

4 ms

ms

m s + 1/2 1/2 Ms

n l m ms


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


1s

2s

2 p

1.


W = V


= | |2

w = | | 2 V

| | 2 | | 2


| | 2

( r ) ( xyz )

3 1

2.


z

s

+

x

z

px

+

x

z

pz

z

py

+

+

x

y


y

y

z

z

x

x

x

x

dxy

dx2y2

s

dz2

z

x

pz

1

2


y

z

z

dxy

dyz

dxz

+

+

+

x

y

x

+

+

+

z

y

+

+

+

x

x

+

d x2y2

d z2


| 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


3d

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


( ) 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


1.

Pauling

ns np

1s

2s 2p

3s 3p

4s 3d 4p

5s 4d 5p

6s 4f 5d 6p

7s 5f 6d 7p


7p

5f

6d

7s

6p

4f

5d

6s

5p

4d

5s

4p

3d

4s

3p

3s

p d f

2p

2s

1s


Li

2

2.

1

+ 3

2

Z Z*


Z* = Z

l

4s 4p 4d 4f

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

n l


2

l

l

n l 3s 3p 3d

l


1

2Pauli

3 Hund

d f p


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


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


* 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


1.

2.


1

H

He

2

Li

Be

B

C

N

O

F

Ne

1.

2

2 1 1s 1

8

8 2 2s 2p 4


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


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


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


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


d

d r=

2.

(2)


Na

r = 154 pm r= 188pm

r>r

( HeNe )


(a)

Z r

r

d5d10f7f14 r


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


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


Li 123 pm

Na 154 pm

K 203 pm

Rb 216 pm

Cs 235 pm

r

(b)

Z r

r


Ti V Cr

r/pm 132 122 118

Zr Nb Mo

145 134 130

Hf Ta W

144 134 130

r

1213 pm

r


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


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


(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


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


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


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


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


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


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


V

0

Vr0

r0

r

r

V

r

Na+ Cl V

r > r0 r

V


q1 q2

r ,F

1

2


2.1 22 83 18418+25 8 18


1 ( Valence Bond Theory )

1927Heitler London H2

Lewis

a

b


E

0

D

ro

R

1

1s

r V

H2

H

1s 2 H

r = r 0 V

E= D ( D > 0 D < 0 )

H


2


3pz

1s

+

+

z

z

+

+

HCl


+

+

z

z

pz

pz

+

+

Cl 3pz H 1s z

Cl 2


+

+

z

z

pz

pz

+

+

Cl 3pz H 1s z

Cl 2


+

+

+

+

3

HCl 3p 1s

Cl 2 3p 3p


x

x

px

+

+

z

180

+

+

  • 180

    px z

YOZ


N2

px py pz

z pz pz px px py py

N2 3 1 2


4

:298.15K1mol


2p

2p

2s

2s

CH4 C

4

4 4 H CH4

AlCl 3 120 NH4+ 10928


Pauling 1931


CH4 2s 2px2py2pz 4 sp3 sp3 s p


+

+

Be sp

2s 2 2p0

1.sp

+

+

=

sp s p 1/2

180

BeCl2

2 sp 2 Cl 3p


BCl 3

B sp2

2. sp2

3 sp2 3 Cl 3p BCl 3


CH4C sp3 4

4 H 1s

CH4

3. sp3


sp3 H 1s

sp3 H2O V

HOH 10928

10445

O

H

H

4.

C sp3 4 sp3

H2O V O sp3


1.

HCl q d = q d


H2O

H2O

BCl3

BCl 3

D

HI HBr HCl NH3 H2O

/ D 0.38 0.79 1.03 1.66 1.85 1.15


2



1.0 10 2 kJ mol1 kJ mol1

1

2


kJmol1

Ar 0 0 8.49

HCl 3.305 1.104 16.82


a )

b )

c )

d ) F 1 / r7

e )

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

3

F 2


1

HF F r

F H H r F H F H

1 r ( FO N ) H

2 r ( FON )


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


CH3CH2OH

H3COCH3

HNO3

3

b. p.

HF HCl HBr HI

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


m. p. 44 45

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

m.p. 113 114


NaCl NaCl

NaCl 58.5



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


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 )



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