Download - 第五章 原子结构和元素周期律
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100 19 20
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1896 Becquerel 1879 Crookes
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1898 Marie Curie 1897 Thomson
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1904 Thomson 1900 Planck
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1909 Millikan 1905 Einstein
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1911 Rutherford
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1913 Bohr
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5. 1 5. 1. 1 1924 de Broglie
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E = mc2 E = h
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mc2 = h
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p p = mc
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p
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p
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1927
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5. 1. 2 F = m a a t
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p = m t = 0 + at
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1927 Heisenberg
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x p x p h
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m x m h
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h h = 6.626 1034 Js
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5. 1 m = 9.11 1031 kg x = 1012 m
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7.27 10 8 ms1
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1010 x = 1012 m
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x
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5. 1
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m = 9.111031 kg h = 6.626 1034 Js
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m = 10 g
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x
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5. 1. 3
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5. 2
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1926 Schdinger
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5. 2. 1
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E V m h
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x + 3 = 5 x = 2
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fx= x2 + C C f x= 2 x f x= x2
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Fxyz
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m V E
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xyz xyz
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r xyz
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x y
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xyz r
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P r OP 0 ~
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OP z 0 ~
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OP x 0 ~ 2OP OP xOy
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r x = r sin cos
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y = r sin sin
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z = r cos
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x = r sin cos y = r sin sin z = r cos r2 = x2 + y2 + z2
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r
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r
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r
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r Rr r = Rr
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R r r
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Y = r = Rr Y Y
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m m
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l l
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R r n n R r
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E n eV
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R Y
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100 200 210
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5. 2. 2 100 200 210 nlm
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1. n 1234 n n KLMN
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n = 1 K n
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n
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E Z eV 1 eV = 1.602 1019 J
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n
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H n = 1 E = 13.6 eV n = 2 E = 3.40 eV
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n E = 0 0
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n 1234 n
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n n
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2. l n l
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n n l 01234 n 1 spdf g
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n = 3 l 012 spd
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l n = 4 l 4 4
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l = 1 p 4p l = 0 s 4s
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l = 2 d 4d l = 3 f 4f
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4 4 n
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M
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M |M| l
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p p = m kgms1 ms1 m kg M M = J s1 J
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M M = J J M p p = m m p
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J m
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r
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J kgm2 M kgm2s1 M = J s1
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p p = m kgms1 ms1 m kg M M = J s1 J kgm2 kgm2s1
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E n l n l
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n l l E
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E l n
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3. m m l m
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l m 0 1 2 3 l 2 l + 1 l = 2 m = 0 1 2 5
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m l p l = 1m 0+ 11 3 p 3
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pz m = 0 2pz 210
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px py m = + 1 m = 1 px py
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m l = 1m 3 3 p
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m 3 2p 3 2p 3
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3d 5 3d 5
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m z Mz
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m 0 1 2 3 l Mz z
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l = 1
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z Mz
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z O
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m = 1 z Mz OAO
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zO
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zOA m = 1A = 45
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m = 1 OB z 135
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m = 0 OC z 90
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m z Mz Mz z
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nlm 3 nlm 2 3 1
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3 5. 2 n = 3 3 nlm
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n = 3 l 012 l = 0 m 1 0 l = 1 m 3 01+ 1 l = 2 m 5 01+ 12+ 2
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nlm 1 + 3 + 5 9
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3 3 3 3 3 3 3 3 30 1 1 12 2 2 2 20 0 +1 10 +1 1 +2 2
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n l m 3 0 03 1 0 3 1 1 3 1 + 132 0 3 2 1 3 2 + 1 3 2 2 3 2 + 2
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4. ms
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Ms
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ms
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Ms
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3 nlm 4 n l m ms
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4 n l m ms
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5. 3 4 n = 4l = 3 l = 3 m = 0 1 2 3 7 7
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nlmms 2 7 = 14
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0 1 1 2 2 3 3 n l m ms 4 3 4 3 4 3 4 3 4 3 4 3 4 3
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0 1 1 2 2 3 3 n l m ms 4 3 4 3 4 3 4 3 4 3 4 3 4 3
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5. 2. 3 1.
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W= V
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| |2 W = | |2 V
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| |2 r
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2.
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2s
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2p
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| |2 r
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| |2
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5. 2. 4 | |2 s p
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| |2
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y = kx + b 1 1 2
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z = ax + by + c 2 1 3
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r xyz 3 1 4
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1. r= RrY r Rr r
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Y r | |2 r | R |2 r
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| R |2 r
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s r 0 | R |2
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2s 1s 3s
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p r 0 | R |2
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2p 1 3p 2
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d r 0 | R |2 3d
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2. r
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1s r
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r
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r r
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| R |2 r W = | R |2 V
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r 4r2 V = 4r2 r
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r W = | R |2 4r2 r W= V
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Dr= 4 r2 | R |2Dr
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Dr r r Dr= 4r2 | R |2
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Dr r 1s Dr= 4r2 | R |2
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Dr = 4r2 | R |2
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Dr = 4r2 | R |2
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Dr r Dr = 4r2 | R |2
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1s Dr= 4r2 | R |2
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1s r = ao
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ao = 53 pm ao
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2s3s
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2s 1s 3s 2s
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2s3s
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Drr O
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1s2s3s2p3p3d
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ns n np n 1 nd n 2
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n l
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n l 1
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1s
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2s2p 1s
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3s3p3d 2s2p
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3.
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a0
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RY
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Y ( ) | Y ( ) | 2 2pz | Y ( ) | 2 = cos2
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2pz 2pz
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5. 3
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n
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n E4s = E4p = E4d = E4f = n E1s < E2s < E3s < E4s <
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n
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5. 3. 1 1.
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2
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+ 3 2
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Z * = Z Z Z *
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l 4s4p4d4f
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n l
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2. l l
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n l 3s
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3s 3p 3d
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l
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n l n n E4s < E3d
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4s 3d E4s < E3d
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E5s < E4d
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3. Pauling
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1s 3s3p 2s2p 5s4d5p 4s3d4p 7s5f6d7p 6s4f5d6p
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1s nsn2fn1dnp
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p d f
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5. 3. 2 1.
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Pauli
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Hunt
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df p
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2.
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* * 6 C carbon 1s2 2s22p2
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7 N nitrogen 1s2 2s22p3
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11 Na sodium 1s2 2s22p63s1 12 Mg magnesium 1s2 2s22p63s2
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* 19 K potassium [Ar] 4s1 ** 21 Sc scandium [Ar] 3d14s2 ** 4s 3d 3d 4s 22 Ti titanium [Ar] 3d24s2 23 V vanadium [Ar] 3d34s2 20 Ca calcium [Ar] 4s2 18 Ar argon 1s2 2s22p63s23p6
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24 Cr chromium [Ar] 3d54s1 25 Mn manganese [Ar] 3d54s2 26 Fe iron [Ar] 3d64s2 27 Co cobalt [Ar] 3d74s2 28 Ni nickel [Ar] 3d84s2 29 Cu copper [Ar] 3d104s1 30 Zn zinc [Ar] 3d104s2 22 Ti titanium [Ar] 3d24s2 23 V vanadium [Ar] 3d34s2
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31 Ga gallium [Ar] 3d104s24p1 32 Ge germanium [Ar] 3d104s24p2 33 As arsenic [Ar] 3d104s24p3 34 Se selenium [Ar] 3d104s24p4 35 Br bromine [Ar] 3d104s24p5 36 Kr krypton [Ar] 3d104s24p6 29 Cu copper [Ar] 3d104s1 30 Zn zinc [Ar] 3d104s2
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37Rbrubidium [Kr] 5s1 38Srstrontium [Kr] 5s2 39Yyttrium [Kr] 4d15s2 40Zrzirconium [Kr] 4d25s2 41Nbniobium [Kr] 4d45s1 42Momolybdenum [Kr] 4d55s1 43Tctechnetium [Kr] 4d55s2 44Ruruthenium [Kr] 4d75s1 45 Rhrhodium [Kr] 4d85s1
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46 Pdpalladium [Kr] 4d105s0 47 Agsilver [Kr] 4d105s1
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Ce 1s22s22p63s23p63d104s24p64d104f15s25p65d16s2 Xe 1s22s22p63s23p63d104s24p64d105s25p6
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57 La lanthanum [Xe] 4f05d16s2 58 Ce cerium [Xe] 4f15d16s2 59 Pr praseodymium [Xe] 4f35d06s2 60 Nd neodymium [Xe] 4f45d06s2 61 Pm promethium [Xe] 4f55d06s2 62 Sm samarium [Xe] 4f65d06s2 63 Eu europium [Xe] 4f75d06s2 64 Gd gadolinium [Xe] 4f75d16s2
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65 Tb terbium [Xe] 4f95d06s2 66 Dy dysprosium [Xe] 4f105d06s2 67 Ho holmium [Xe] 4f115d06s2 68 Er erbium [Xe] 4f125d06s2 69 Tm thulium [Xe] 4f135d06s2 70 Yb ytterbium [Xe] 4f145d06s2 71 Lu lutetium [Xe] 4f145d16s2
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74 W tungsten [Xe] 4f145d46s2 75 Re rhenium [Xe] 4f145d56s2 76 Os osmium [Xe] 4f145d66s2 77 Ir iridium [Xe] 4f145d76s2 78 Pt platinum [Xe] 4f145d96s1 79 Au gold [Xe] 4f145d106s1 80 Hg mercury [Xe] 4f145d106s2 72 Hf hafnium [Xe] 4f145d26s2 73 Ta tantalum [Xe] 4f145d36s2
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13 2429 414244454647 575864 7879
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5. 3. 3 Werner
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1.
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2 1 1s 1 2
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8 2 1 2s 2p 8 4 3
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2 1 3s 3p 8 4 3 8
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3 1 4s 4p 18 9 3 18 3d 5
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3 1 5s 5p 18 9 3 18 4d 5
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4 32 16 32
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4 32 16 32
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Cr [ Ar ] 3d5 4s1 3d5 4s1 Cr
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2.
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f
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s IA IIA
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12 ns1 ~ 2
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p IIIA IVA VA VIA VIIA 0 VIIIA
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13 18 6 ns2 np1 ~ 6
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p
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s p s p
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8 0 VIII A
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d III B IV B V B VI B VII B VIII
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3 10 8 n1d1~ 10 ns0 ~ 2
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d n1d
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456
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La
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d n1d ns
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8 VIII
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ds I B II B
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1112 n1d10 ns1~ 2
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ds ns
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ds d
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f f n2f 0 ~ 14 n1 d0 ~ 2 ns2
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f n2f f III B
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K E4s < E3d 4s E4s < E 3d 5. 3. 4
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Cu Cu+ 4s E4s > E3d
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1 Z = 1
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Ens = Enp = End = Enf
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2 Z > 1 Z
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3 n l
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l Ens < Enp < End < Enf
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4
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1 ~ 14 E4s > E3d
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15 ~ 20 E4s < E3d
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21 E4s > E3d
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Cu E4s > E3d K E4s < E3d
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5. 3. 5 Slater
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E
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1
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2s 2p3s 3p = 0
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2 = 0.35 1s = 0.30
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3ns np n1 = 0.85 n2 = 1.00
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4ndnf = 1.00
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5. 4 K 19 3d 4s
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3d 4s
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4s 4s =+ 1.00 10= 16.8 0.85 8
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4s = 16.8 = 4.11 eV
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3d 3d =1.00 18 = 18
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= 1.51 eV 3d = 1.00 18 = 18
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E4s < E3d K 4s E4s = 4.11 eV E3d = 1.51 eV K 1s2 2s2 2p6 3s2 3p6 4s1
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Fe 1s2 2s2 2p6 3s2 3p6 3d6 4s2 5. 5 Fe 26 3d 4s
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4s =+ 1.00 10+ 0.85 140.35 1= 22.25
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= 11. 95 eV 4s = 22.25
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3d == 19.75 + 1.00 180.35 5
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= 59.03 eV 3d = 19.75
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Fe E4s > E3d 4s E4s = 11.95 eV E3d = 59.03 eV
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ns np
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5. 4
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5. 4. 1 1 1.
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2 r
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r > r
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3
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2. 1
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Z r r
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d5d10f7f14 Z
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d5d10f7f14 r
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3 Na S6 r 80 pm 16 pm
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4 Sc Ni8 r 38 pm 5.4 pm
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CuZn d10 r
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16 pm 5.4 pm
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Z* r
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Z* r
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Yb 4f14 6s2f r/pm 183 182 182 181 183 180 208 180 r/pm 177 176 176 176 176 194 174 Eu 4f7 6s2f
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r/pm 183 182 182 181 183 180 208 180 r/pm 177 176 176 176 176 194 174 Eu Yb r
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15 r 9 pm
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n2f Z* r
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r/pm 183 182 182 181 183 180 208 180 r/pm 177 176 176 176 176 194 174 15 9 pm
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15
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Zr Nb Mo Tc Rur/pm 160 146 139 136 134 Hf Ta W Re Osr/pm 159 146 139 137 135
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2 Z r r
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Z r r
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IA Li 152 pm Na 186 pm K 232 pm Rb 248 pm Cs 265 pm
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r /pm Ti 147 V 134 Cr 128 Mn 127 Fe 126 Zr 160 Nb 146 Mo 139 Tc 136 Ru 134 Hf 159 Ta 146 W 139 Re 137 Os 135 r 10 pm
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r r /pm Ti 147 V 134 Cr 128 Mn 127 Fe 126 Zr 160 Nb 146 Mo 139 Tc 136 Ru 134 Hf 159 Ta 146 W 139 Re 137 Os 135
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5. 4. 2 1.
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E1s = 13.6 eV = 0 eV
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E = 0 eV 13.6 eV E1s = 13.6 eV = 13.6 eV E = 0 eV
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eV 1 eV W = 1.602 1019 C 1 V = 1.602 1019 J 1 1.602 1019 C 1V
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E = 1.602 1019 J 13.6 6.02 1023mol1 = 1312 kJmol1
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1 mol 1 mol 1 mol M+ I1
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1 mol M+ 1 mol 1 mol M2+ I2 I3I4 In
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1 mol H 1312 kJmol1 kJmol1
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1s
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2. Z r 1 I1
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I1 /kJmol1 Li Be B C N O F Ne 520 900 801 1086 1402 1314 1681 2081
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I1 / kJmol1 Li Be B C N O F Ne 520 900 801 1086 1402 1314 1681 2081 I1Be> I1B I1N > I1O
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B [ He ] 2s2 2p1 2p Be 2s2 I1 Be I1Be> I1B
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N [ He ] 2s2 2p3 2p3 I1 O I1N > I1O
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O [ He ] 2s2 2p4 2p4 2p3 I1 N
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Ne [ He ] 2s2 2p6 I1 /kJmol1 Li Be B C N O F Ne 520 900 801 1086 1402 1314 1681 2081
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I1 /kJmol1 Sc Ti V Cr Mn Fe Co Ni Cu Zn 633 659 651 653 717 762 760 737 746 906 Z
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Zn [ Ar ] 3d10 4s2 Zn I1 I1 /kJmol1 Sc Ti V Cr Mn Fe Co Ni Cu Zn 633 659 651 653 717 762 760 737 746 906
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2
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Z I1 r I1
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I1 /kJmol1 Be 900 Mg 738 Ca 590 Sr 550 Ba 503
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Ti V Cr Mn Fe Co Ni Cu Zn 659 651 653 717 762 760 737 746 906 I1 /kJmol1 Zr Nb Mo Tc Ru Rh Pd Ag Cd 640 652 684 702 710 720 804 731 868
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I1 /kJmol1 Zr Nb Mo Tc Ru Rh Pd Ag Cd 640 652 684 702 710 720 804 731 868 Hf Ta W Re Os Ir Pt Au Hg 659 728 759 756 814 865 864 890 1007
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3. Z* r
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I1 < I2 < I3 < I4 <
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In /kJmol1
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I1 I2 I3 I4 I5 I6 Li 520 7298 11815 Be 900 1757 14849 21007 B 801 2427 3660 25026 32827 C 1086 2353 4620 6223 37830 47277 N 1402 2856 4578 7475 9445 53267
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B I1I2 I3 B I1 I2 I3 I4 I5 B 801 2427 3660 25026 32827
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B 1s2 2s2 2p1 3 I1 I2 I3 I4 I5 B 801 2427 3660 25026 32827
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I4 I1 I2 I3 I4 I5 B 801 2427 3660 25026 32827
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I1 I2 I3 I4 I5 B 801 2427 3660 25026 32827 I2 I1 = 1626 kJmol1 I3 I2 = 1233 kJmol1 I4 I3 = 21366 kJmol1
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I1 I2 I3 I4 I5 B 801 2427 3660 25026 32827
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BIV BIII LiIBeIICIV NV
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1. 5. 4. 3 1 mol 1mol M E1 E2E3E4
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Fg+ e = Fg H = 328 kJmol1 E1 = H = 328 kJmol1
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E H
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2. Z r E
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B C N O FE /kJmol1 27 122 141 328 E
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E B C N O FE /kJmol1 27 122 141 328
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N [ He ] 2s2 2p3 2p B C N O FE /kJmol1 27 122 141 328
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N B C N O FE /kJmol1 27 122 141 328
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F
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F E
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O S Se
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F Cl F2 Cl2 ?
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F2 Cl2
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F2 Cl2
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|H5| > | H6 | F2 Cl2
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5. 4. 4 I E
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1932
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4
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Li Be B C N O F 0.98 1.57 2.04 2.55 3.04 3.44 3.98
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F 3.98 Cl 3.16 Br 2.96 I 2.66 Li 0.98 Na 0.93 K 0.82 Rb 0.82 Cs 0.79
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F Cs
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< 2.0 > 2.0
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1934 Mulliken
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1957 Allred Rochow