2019*- ? SK+&oec.chembio.nagoya-u.ac.jp/PDFs/2019_HU_MainGroup/MGC_01_handout.pdfDmitri Mendeleev...
Transcript of 2019*- ? SK+&oec.chembio.nagoya-u.ac.jp/PDFs/2019_HU_MainGroup/MGC_01_handout.pdfDmitri Mendeleev...
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2019 @Main Group Chemistry
1,2
13,1415,16
17
( ) ( ) I
2ISBN; 9784807908202
( ) ( )
ISBN; 9784807905874W. Henderson( ) ( )
( )ISBN: 9784759810042
( ) (11)
( ) ISBN:9784000110419
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Dmitri Mendeleev
Periodic Table of Elements
(period)
the 1stthe 2ndthe 3rd
(group)
![Page 3: 2019*- ? SK+&oec.chembio.nagoya-u.ac.jp/PDFs/2019_HU_MainGroup/MGC_01_handout.pdfDmitri Mendeleev Periodic Table of Elements (period) the 1st the 2nd the 3rd (group)](https://reader033.fdocuments.in/reader033/viewer/2022042020/5e771bb88f2c7b2c9440a542/html5/thumbnails/3.jpg)
(Main Group Element)
11,12
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Ionization Energy (IE) =
E(g) → E+(g) + e− DH
IEIE
2 (ns2) 13 (ns2np1) IE →15 (ns2np3) 16 (ns2np4) IE →
11ISBN 978-4000110419
2 13
15 16
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Electron Affinity =
E(g) + e− → E−(g) DH
Emsley, J., The Elements; Oxford University Press: New York, 1998.
0 or17 ( )
1 (ns1) 14 (ns2np2) EA→
0
50
100
150
200
250
300
350
400
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35
(kJ/
mol
)
H
He
Li
Be
B
C
N
O
F
Ne
Na
MgAl
Si
P
S
Cl
Ar
K
Ca
Sc
Ti
VCr
Mn Fe
CoNi Cu
ZnGa
Ge
As
Se
Br
Kr
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Linus C. PaulingNobel Prize1954
Electronegativity =
11ISBN 978-4000110419
PaulingMullikenAllred Rochow
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(covalent radius)→→
→→
→
Online Textbook: Atomic Structure and the Periodic Tablehttp://www.chem1.com/acad/webtext/atoms/index.html
WebElements: the periodic table on the webhttp://www.webelements.com/
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Albert EinsteinNobel Prize1921
m0 vm (c= )
Pyykko, P., Chem. Rev. 1988, 88, 563-594.
―
ISBN 978-4807913442
a0a0
e0: , ħ: Planck , me: , e:
4 p e0 ħ
[v=Zc/137; Z= ]
4f 5d 6p
→
1s2s 2p3s 3p 3d4s 4p 4d 4f5s 5p 5d 5f 5g6s 6p 6d 6f 6g 6h7s 7p 7d 7f 7g 7h
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ns
np
ns
np
ns
np
ns
np2s,2p3s,3p3s,4s
→5s 6s
→
Pyykko, P., Chem. Rev. 1988, 88, 563-594.
―
ISBN 978-4807913442
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→
―
ISBN 978-4807913442
2s 2p sp ns np sp
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= 1s 2yb ya
11ISBN 978-4000110419
p
ps, s* p, p*
2 2→
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( )
(= )
Pauling
X M
I p302
Xδ– Cδ+
X = N, O, F, Cl, (S,) Se, Br, (I)Mδ+ Cδ–
M =
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(1)
(oxidation #)
= =
= 2 2 2
=
1. +1 −12.
=(1) +1 ( : NH4
+)(2) ( : CMe4)(3) ( : CH2Cl2)
Parkin, G., J. Chem. Edu. 2006, 83, 791-799.
(valency, valence)
Karen, P.; McArdle, P.; Takats, J., Toward a comprehensive definition of oxidation state (IUPAC Technical Report). In Pure Appl. Chem., 2014; Vol. 86, p 1017.
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(2)
Parkin, G., J. Chem. Edu. 2006, 83, 791-799.
(# of bonds)
(coordination #)
= 2 2
=
2 2, 3 3
=
=
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VSEPR
(valence shell electron pair repulsion rule)
W. Henderson( ) ( )( )
→1) Lewis2) p 13) 4)
LP >LP BP>BP(LP: lone pair, BP: bonding pair)
SF4
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(hypervalent compounds)=
PF5(1) (eq) sp2
(2) (ap) pp
3 4(3) eq ap
―
ISBN 978-4807913442 Chemistry of Hypervalent CompoundsKin-ya Akiba Ed., Wiley-VCH, 1999
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William LipscombNobel Prize1976
Be(CH3)2
CH5+ B2H6
W. Henderson( ) ( )( )
―
ISBN 978-4807913442
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I p303
Charles PedersenNobel Prize
1987
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→( p10 )
sp3
( )
sp3
=
TlCl, SnCl2, PbCl2, GeCl2(dioxane)
TlR, PbR2
14
―
ISBN 978-4807913442
ener
gyen
ergy
2s
2psp3 sp3
C(no hybridization)
CX4(sp3)
C(sp3)
ΔEprom
ΔEbond
ener
gyen
ergy
ns
npsp3 sp3
E(no hybridization)
E(sp3)
EX4(sp3)
ns
np
EX2(no hybridization)
ΔEprom ΔEbond
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Science 1981, 214, 1343-1344.
J. Am. Chem. Soc. 1981, 103, 4587-4589.
Science 2004, 305, 1755-1757.R = 2,4,6-Me3C6H2
R = 2,4,6-tBu3C6H2
R = Si(CHSiMe3)2iPr
―
ISBN 978-4807913442
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Wittig
b-
I p343-347
Georg WittigNobel Prize
1979
P CHH
PhPh
Ph
σ*PC
C CRR
RR
R3Si
σSiC
C N
σCN
σ*CN
2p 2pC
P
σCP
σ*CP
2p3p