040813F 14 2 27
3 I 5 I.1... 5 I.2... 5 I.3... 5 I.3.1... 5 I.3.2... 5 I.3.3... 7 I.4... 7 I.4.1... 7 I.4.2 (Electron Affinity)... 8 I.5 (electronegativity)... 9 I.5.1... 9 I.5.2... 9 I.5.3... 10 II 13 II.1... 13 II.1.1... 13 II.1.2... 13 II.1.3... 16 II.1.4 / (HSAB)... 17 II.2... 19 II.2.1... 19 II.2.2... 19 II.2.3 ( )... 20 III 25 III.1... 25 III.2 ( )... 25 III.3... 29 III.4... 29 III.4.1 ( )... 30 III.4.2... 31 IV (Coordination Chemistry) 33 IV.1 (transition metal)... 33 IV.2... 34
4 IV.2.1... 35 IV.3 (d )... 36 IV.3.1 d LFSE d... 36 IV.3.2... 37 IV.3.3 d... 37 IV.4... 40 IV.4.1... 40 IV.5... 41 V 43 V.1... 43 V.2... 44 V.3... 44 V.4... 45 V.5 13... 45 V.6 14... 46 V.7 15... 46 V.8 16... 47 V.9 17... 47 V.10 d... 47 V.10.1... 48 V.10.2... 48 V.11 f... 48 V.11.1... 48 V.11.2 (57 La - 71 Lu)... 48 V.11.3 (89 Ac - 103 Lr)... 49 VI ( ) 51
5 I I.1 ( ) I.2 : Ge Sn I.3 I.3.1 I.3.2 (1) (2) ( ) O 2 (6 ) 1.26Å 1 1 Shannon Pauling
6 I (3) ( ) ex.) N 3+ 16pm N 75pm N 3 171pm P 3+ 44pm P 106pm P 3 171pm < < ( ) r ion (cation) <r con <r ion (anion) <r VDW 2 1s r max = 2 2Z a 0 2p r max = 4 2 2Z a 0 2 r max D(r) =r 2 R 2 n,l ( ) R 2 n,l d D(r) =0 rmax dr
I.4. 7 3d r max = 6 3 2Z a 0 Z Z I.3.3 K Ca Cr Cu Ge 203 194 118 117 122 Rb Sr Mo Ag Sn 216 191 130 134 140 Cs Ba W Au Pb 235 198 130 134 147 4d 5d 4f 4f 3 I.4 I.4.1 1 1 ( ) ev 4 ( I.1) H H 1s 1 +2 He He + +e 24.6eV He + He 2+ +e 54.4eV He He 2+ +2e 79.0eV 3 f 4 SI 1[eV] = 1 1.602 10 19 [C : ] 6.02 10 23 [1/mol : ] = 96480[J/mol]
8 I E(eV) -13.6-39.5 H1s?? He -54.4 He + 1s I.1: He 1 79.0 =39.5[eV] 2 24.6eV 54.4eV < > ( ) ( ) I.4.2 (Electron Affinity) A(g)+e (g) A (g) [ev] ( I.2) H e H e = A e
I.5. (electronegativity) 9 I.2: ( )! I.5 (electronegativity) a a I.5.1 = (covalent) + (ionic) D A,B D(AB) = D(AA) D(BB)+ : A B χ χ A χ B =0.208 H:χ H =2.1 I.5.2 χ AR =0.74 + 0.36 Z ef f r 2 r : (Å) 5 5 r Z eff
10 I (I) (A e ) LUMO( ) HOMO( ) I.3: E H1s Cl 2p I.4: HCl I.5.3 χ M = I + A e 2 [ev] 6 ( I.3) 7 LUMO HOMO ) HCl 6 χ P =0.336χ M 0.207 7 ( I.3) LUMO,HOMO
I.5. (electronegativity) 11 Φ antibonding = C 1 φ H1s C 2 φ Cl2p C 1 C 2 Φ bonding = C 1 φ H1s + C 2 φ Cl2p C 1 C 2 Cl H + Cl (?)
13 II II.1 II.1.1 (H + ) (OH ) II.1.2 NH 3 ( ) ( ) conjugate acid ex.) HA+H 2 O H 3 O + +A HA H 2 O H 3 O + A B-acid( ) B-base C-acid( ) C-base 1 H 2 O HSO 4 H + 1
14 II (1) HA+H 2 O A +H 3 O + K a = [A ][H 3 O + ] [HA] pk a = log K a 2 < 0(K a = ) ( ) pk a > 0 H 3 O + +H 2 O H 2 O+H 3 O + K a =0( ) HA H 3 O + H 3 O + ( )H 3 O + K a ( HA 0 ) K a = [A ][H 3 O + ] [HA] 0 = HA H 3 O + ( H 3 O + ) ( OH ) a a HClO 4,HBr,H 2SO 4,HNO 3 HClO 4 >HBr>H 2SO 4 >HNO 3 ( ) 2 10
II.1. 15 (2) BH + +OH B+H 2 O H 2 O+OH OH +H 2 O pk b = log [BH+ ][OH ] [B ] (K b =1,pK b =0) < 0(K b =,pk b < 0) = > 0 10 14 pk b < 0 pk a > 14 pk a < 0 0 <pk a < 14 pk a > 14 2HX H 2 X + +X 3 K =[H 2 X + ][X ] 4 ( ) ph < >(acidity) ph = log[h 3 O + ] B( a ) H 0 = pk BH + log C BH + C B (B+H + BH + ) pk BH + BH + K BH + = [B][H+ ] [BH + ] a ( ) ( ) 3 K am =10 24 4 X=OH K = K w
16 II H + C BH + =[BH + ],C B =[B] H 0 = log [B][H+ ] [BH + log [BH+ ] ] [B] = log[h + ] log [B] [BH + ] [BH+ ] [B] = log[h + ] = ph H 0 = ph log [B]C BH + [BH + ]C B ( ) II.1.3 / = a = a H + 1 H + +NH 3 NH 4 + 2 Ag + +2NH 3 [Ag(NH 3 ) 2 ] + 3 BF 3 +NH 3 BF 3 NH 3 BF 3 2 NH 3 4 CO 2 +OH HCO 3 5 5
II.1. 17 H X Y II.1: K HX H K HY X Y II.2: 5 ( ) ( ) ( ) 6 KI I 2 I p 3 4 II.1.4 / (HSAB) HSAB : Hard and Soft Acids and Bases K a H + =(H + ) ( II.1) H + X Y K HX = [HX] [H][X],K HY = [HY] [H][Y] 6 ( II.2) H + A+X K f AX K f = [AB] [A][B] 7 K f 6 K a = KHY K HX Y=OH 7 affinity
18 II P Q X Y X II.3: HSAB Y (1) ( a ) (2) ( b ) ( ) a (K f ) (3d, ) Ti 4+,Co 3+,Fe 3+ Al 3+,H +,BF 3 b (K f ) (4d,5d,, )(Pt 2+, Pt 4+, Au 3+,Ag +,Cu + etc,),i 2 a a F Cl> Br> I O S N P b 8 ( II.1) r r 8
II.2. 19 II.2 II.2.1 ( ) a a! (1) =0 (2) = (3) (4) (H,F a,o) a F 1 ( ) O 2 H 1 II.2.2 Ox Red 9 ( ) II.1:? NH 3, NR 3 ( ), H 2 O, R 2 O, OH,F PR 3 ( ), R 2 S( ), S 2,I 9
20 II II.4: Red 1 Ox 1 +e Ox 2 +e Red 2 Ox 1 /Red 1 Ox 2 /Red 2 10 ( )! ) Zn 2+ +2e Zn Zn 2+ /Zn II.2.3 ( ) 11 ( ) = G = RT ln K<0 12 2H + +2e H 2 G H + /H 2 =0 10 Ox/Red 11 2Fe 3+ +Cu 2Fe 2+ +Cu 2+ ( Fe 3+ +e Fe 2+ E ) 12 ( ) 1atm (298K ) ph 1 1
II.2. 21 E E 1 Ox 1 +n 1 e Red 1 e ( ) E 2 Ox 2 +n 2 e Red 2 ( ) II.5: G Ox/Red = nf E n F E (V) (96480C/mol) ( II.5) G all = n 2 G 1 n 1 G 2 = n 1 n 2 FE1 ( n 1n 2 FE2 ) = n 1 n 2 F (E1 E 2 ) E 1 E 2 > 0, G all < 0 2H + (aq)+2e H 2 (g) E H + /H 2 =0 ( II.7) ( ) G 0 Ox+ne Red E Ox/Red ( ) 2Cu + Cu 2+ +Cu, 2Fe 3+ +Fe 3Fe 2+ ( II.5) (E ) ( )
22 II 1atm H 2 Pt 1.18M HCl H + =1 II.6: (SHE) G II.7:
II.2. 23 (E ) case by case
25 III III.1 ( ) C, SiO 2,NaCl ( ) ( III.1) T g 1 = III.2 ( ) 2 ccp (cubic closest packing) hcp (hexagonal closest packing) fcc (face-centered cublic) A B C A B 12 12 cuboctahedron ( ) anti cuboctahedron ( ) Cu,Ag,Au,Ne,Ar Be,Mg,Zn,Cd,Co,He C A 1 B C A 2 1
26 III T g T m III.1: T III.2: A B ( III.2) 2 C 2
III.2. ( ) 27 III.3: ( interstitial site) (O-Site 3 ) (T-site 4 ) (III.3) ( ) ( ) = 1 8 8+1 2 6=4( ) ( III.4) O-site 1 1+ 1 12 = 4( ) 4 T-site ( III.4 8 1 8=8( ) T-site O-site ( ) 1 6 12 + 1 2+1 3=6( ) 2 ( ) O:6,T:12 ( III.5) 3 Octahedral site 4 Tetrahedral site
28 III III.4: O-site,T-site III.5: O-site,T-site
III.3. 29 III.1: hcp,fcc 12 anti-cuboctahedron, cuboctahedron 74% bcc 8 cube 68% sc 6 octahedron 52% 4 tetrahedron 35% sp 3 O-site 1 6 12 + ( )1 2+( )1 3=6 2 T-site 1 3 2( )+1( ) 2+ 1 ( ) 6 2=12 3 III.3 (body-centered cubic (bcc)) 8 5 ex.)li,na,k,sr,cs,ba (simple cubic (sc)) 6 ex.) α Mn T-site 4 ex.) C, Si ( III.1) III.4 5
30 III ( 6 ) III.4.1 ( ) O-site T-site / O-site ( ) T-site ( ) ccp(fcc) (NaCl) (Zinc Blende) hcp (NiAs) ( ) NaCl ccp(fcc) 6 ( ) O-site 6 fcc 4 ccp(fcc) 4 T-site 4 fcc fcc 4 ( 1 4, 1 4, 1 ) 4 hcp 6 (trigonal prism) 7 O-site 6 6 hcp 4 T-site 4 8 6 7 ( ) 8 1 6+1 3+1 1=6 3
III.4. 31 6 hcp fcc bcc hcp fcc, bcc III.4.2 U := 0K 1mol U Born r 0 U(r 0 ) Coulomb 9 U = E c ( )+E r ( ) (A) NaCl (fcc ) Na( ) Cl( ) 6 r Na 12 2r Cl 8 3r Na 6 2r E c = 6e2 r (Z+ )(Z )+ 12e2 (Z + ) 2 + 8e2 (Z + )(Z )+ 6e2 2r 3r 2r (Z+ ) 2 + = e2 Z 2 ( 6 12 + 8 6 ) r 2 3 2 + = e2 Z 2 A r 9 ( )
32 III A NaCl 1.747558, CsCl 1.762670 b exp( ar) U = N A ( A(Z + )(Z )e 2 r ) + b exp( ar) r 0 U r0 ( ) ( U A(Z + )(Z )e 2 ) =0=N A r r=r 0 r0 2 ab exp( ar 0 ) b b b = A(Z+ )(Z )e 2 exp(ar 0 ) r 0 2 a (III.1) U r0 = AN A(Z + )(Z )e 2 r 0 ( 1 1 ) r 0 a (III.1) NaCl Z + =1,Z = 1,a=2.90 10 8 cm 1,r 0 = 2.814Å,U r0 = 756.6kJ/mol
33 IV (Coordination Chemistry) d := A B C B C A ( ) IV.1 (transition metal) d 1 3d K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn 3d 0 0 1 2 3 5 5 6 7 8 10 10 4s 1 2 2 2 2 1 2 2 2 2 1 2 d s d ( IV.1) 3d 4s 3d 4s 3d 4s 4s 2 E 4p 4 4s 3d IV.1: 3d, 4s, 4p 1 d 2 3d 3d 4s 4s 3d
34 IV (Coordination Chemistry) A δ δ + B A B A B IV.2: 3d 3d 4s d p ( ) d IV.2 := (lone pair) ( ) ( ) ( 3 ) ( ) 3d 6 4d, 5d 6 ( IV.2) A LUMO B HOMO B A A A B 4 3d 4d 4d 5d 3d 4d, 5d 5 3d 4d, 5d 3 ligand( ) 4 CO Fe Fe 3d CO π (Fe(CO) 5 ) π 5 6 6 6
IV.2. 35 HSAB (early transition metal) (later transition metal) O 2,F S 2,I 3d 4d 5d IV.2.1 (:NH 2 NH + 3 ) H 2 O, NH 3 Cl,OH,F,Br ( ( ) ) 1 H 2 O, NH 3,Cl,OH, 2 (H 2 N-CH2 -CH 2 - NH 2 ) 3 6 acac( 7 ) tmen(n, N, N,N - 8 ) 9 1,10- H + 6 7 2,4-8 ( : edta) COO O 6 9
36 IV (Coordination Chemistry) 0.6 o 0.4 o ( ) IV.3: d o IV.3 IV.3.1 (d ) d LFSE d d ( ) (x,y,z 6 ) 2 (P g :d x 2 y 2,d z 2) 3 (t 2g: d xy,d yz, d zx ) (( IV.3) ) 2 3 d x 2 y 2 z d z 2 x, y 45 10 ( IV.3) o 11 0.6 o,0.4 o [Cr(NH 3 ) 6 ] 3+,Cr 3+,d 3 (d 3 ) t 2g 3 ( 0.4 o ) 3= 1.2 o Crystal Field Stabilization Energy ( ) (CFSE) Ligand Field Stabilization Energy (LFSE) d LFSE ( IV.4) d 5,d 10 d ( IV.5) ( )Ca 2+,Zn 2+ ( IV.4) LFSE 12 H + 10 11 o Octahedral o 12 H 2O
IV.3. (d ) 37 LFSE(CFSE) 1.2 O 0 1 2 3 4 5 6 7 8 9 10 IV.4: d LFSE d M 2+ Ca 2+ (d 0 ) Mn 2+ (d 5 ) Zn 2+ (d 10 ) IV.5: LFSE IV.3.2 d ( ) IV.3.3 d ( IV.6) LUMO e g t 2g d t 2g t 2g ( IV.7) ( )
38 IV (Coordination Chemistry) t 1u a 1g e g t 2g (n+1)p (n+1)s nd non-bonding MO t 1u a 1g e g e g t 2g e g t 1u e g t 1u a 1g a 1g M( ) ML 6 L( ) 6 IV.6: ( ) IV.7: 2+3 ( IV.8) ( ( IV.9) 13 ) o t 4 9 o t 2 e t IV.8: d-d 13 t 2
IV.3. (d ) 39 p s t 2 a 1 t 2 a 1 anti-bonding d t 2 t 2 e t 2 t 2 a 1 a 1 non-bonding bonding M ML 4 4L IV.9: ( ) t 2 t 2 t 2 d (d yz, d zx, d xy) p ( ) 3 ( d p d p xyz 1 3 ) d p d p d p d p
40 IV (Coordination Chemistry) IV.4 ( ) CO, CN > phen a > NO 2 > o-phen > dipy b > en c > NH 3 > NCS d > H 2 O > F > RCO 2 > OH > Cl > Br > I a 1,10- b c d C > N > O > d 3d < 4d < 5d 4d 5d 3d 4d M II < M III 14 IV.4.1 (1) 14?(?)
IV.5. 41 (2) 1 1 ( P )2 2 P< ( ) 1 low spin configuration P> ( ) 2 high spin configuration IV.5 (1) K f,hsab / 0.1mol/l at 25 1 / (labile) e g, d 0 d 2 [Cu(H 2 O) 4 ] 2+ NH 3 [Cu(NH3 ) 4 ] 2+, [Ni(H 2 O) 6 ] 2+ (d 8 ), [Fe III (H 2 O) 6 ] 3+ (d 5, t 3 2g,e 2 g ), [V(phen) 3 ] 3+ (d 2 ) (inert) d 4,d 5,d 6 low spin, d 3 M III [Cr III (H 2 O) 6 ] 3+ Cl [Cr III Cl(H 2 O) 5 ] 2+ [Cr III Cl 2 (H 2 O) 4 )] + ( ), [Fe III (CN) 6 ] 3 (d 5 low spin), [Co III (NO 3 ) 6 ] 3 (2) ( )
43 V V.1 3 H 99.984% D( 2 H) 0.010156% T( 3 H) 10 18 % D T ( ) (NMR) 1 2 ( ) ( ) H 2 +X 2 2HX ) (1) H 3 O +, ClO 4, Na+ H (2) (3) H H H B B H H H H ( ) (4) 1 MRI 2 13 C
44 V V.1: He Ne Ar Kr Xe Rn (Å) 0.93 1.12 1.54 1.69 1.90 2.2 (kj) 24.58 21.56 15.76 14.0 12.13 10.75 V.2 ( V.1) 6XeF 4 +2H 2 O 2XeO 3 +4Xe+3O 2 + 24HF V.3 1 M + (cf. ) 4Li + O 2 2Li 2 O 2Na + O 2 Na 2 O 2 K+O 2 KO 2 2M + H 2 2MH ( )
V.4. 45 ( ) Li Mg, Be Al, Na Ca, B Si V.4 p CaCl 2 3 CaC 2 +2H 2 O Ca(OH) 2 +C 2 H 2 CaC 2 : V.5 13 B SP 2 In Tl Al cf.) 4 Cr Fe Al,Ga,In 15 (As, Sb, N) III-V GaAs 5,GaN 6 Zinc blende ( ) 3 4? 5, LED, 6 LED,
46 V PN PN V.1: PN ( ) V.6 14 { C, Si, Ge Sn, Pb C C : (sp 3 ), (sp 2 ), C 60 (sp 3 ), Si SiO 2 +2C 2CO+Si Si + 3HCl SiHCl 3 +H 2 SiHCl 3 +H 2 Si + 3HCl 7 :? LED ( V.1) ( ) Ge V.7 15 N 2 NX 3 ( ) 7
V.8. 16 47 V.8 16 ( ) 8 M OH MO +H + )BO 3 3, CO2 3, SiO4 4, NO 3, PO3 4, SO2 4, S 2O 2 4, ClO 4, BrO 3 S 8 S 2 X 2, SX 2, SX 4, SX 6 etc. V.9 17 X X 2 H CaF 2 SO 4 2 HF F 2 NaCl + H 2 O Na + +OH + 1 2 Cl 2 + 1 2 H 2 : ClF, ClF 3,IF 5,IF 7 ( I, F, F) : HClO( ) <HClO 2 ( ) <HClO 3 ( ) <HClO 4 ( ) V.10 d (1) (I) (II) (III) (2) 9 (3) (4) 8 9
48 V V.10.1 Li,Cs,Rb,K,Ba,Sr,Ca,Na,La( )/Mg,Be,Al,Zn,Cr,Fe( )/ Cd,Co,Ni,Sn,Pb,(HCl )/(H) Cu, Hg, Ag, Pd, (HNO 3 )/ Pt, Au ( ) 10 ( 11 ) V.10.2 (Cu, Sn), (Cu, Zn), (Cu, Ni, Zn), (Cu, Mn, Mg, Al), (Fe, Cr, Ni), (Ni, Cr, Fe, Mn) V.11 f V.11.1 12 V.11.2 (57 La - 71 Lu) 4f ( 6s ) 4f 4d/5d ( : Eu(III)) f-f Eu(III):, Tb(III):, Ce(III): f-f (Sm 2 Co 17, Nd 2 Fe 14 B( )) (LaNi 5 ) (La 2 O 3 ) 10 11 chno01.tex 12 ( )
V.11. f 49 V.2: 3 La 57 [Xe]5d 1 6s 2 [Xe] +3 107.7 Ce 58 [Xe]4f 1 5d 1 6s 2 [Xe] 4f 1 +2,+3,+4 103.4 Pr 59 [Xe]4f 3 5d 1 6s 2 [Xe]4f 2 +3,+4 101.3 Nd 60 [Xe]4f 4 5d 1 6s 2 [Xe]4f 3 +2,+3,+4 99.5 Pm 61 [Xe]4f 5 5d 1 6s 2 [Xe]4f 4 +3 97.9 Sm 62 [Xe]4f 6 5d 1 6s 2 [Xe]4f 5 +2,+3 96.4 Eu 63 [Xe]4f 7 5d 1 6s 2 [Xe]4f 6 +2,+3 96.4..... Yb 70 [Xe]4f 13 5d 1 6s 2 [Xe]4f 13 +2,+3 85.8 Lu 71 [Xe]4f 14 5d 1 6s 2 [Xe]4f 14 +3 84.8 (La 1 x Sr x CoO 3 ) ( V.2) V.11.3 (89 Ac - 103 Lr) 5f
51 VI ( ) PHS : 1 2 5 1 ( VI.1) (1) ( VI.1) (2) (I) (II) Fe 3+ +3e Fe Cu 2+ +2e Cu (3) (III) 2 (1) (2) (3)
52 VI ( ) VI.1: E 0 (V) F 2 +2e 2F +2.87 MnO 4 +8H + +5e Mg 2+ +4H 2 O +1.51 Cl 2 +2e 2Cl +1.36 O 2 +4H + +4e 2H 2 O +1.23 Br 2 +2e 2Br +1.09 Fe 3+ +e Fe 2+ +0.77 I 2 +2e 2I +0.53 Cu + +e Cu + +0.52 Cu 2+ +e Cu +0.15 2H + +2e H 2 0 Fe 2+ +2e Fe 0.45 Zn 2+ +2e Zn 0.76 Mg 2+ +2e Mg 2.37 Li + +e Li 3.04 3 ( VI.1) 1:1 (1) 2 ( VI.1), ( VI.1) (2) ( ) (3) (2)
53 VI.1: (fcc) VI.2: log K 1 Hg 2+ Fe 3+ F 1.03 5.20 Cl 6.74 0.66 Br 8.94 0.21 I 12.87 4 K 1 M+L ML K 1 =[ML]/[M][L] Hg 2+ Fe 3+ log K 1 ( VI.2) (1) ( VI.2) Hg 2+ Fe 3+ (2) ( VI.2) Hg 2+ Fe 3+ (3) d (4) [AgCl 2 ] +2HI [AgI 2 ] +2HCl
54 VI ( ) 5 (1) 103 1 2 (2) (1),, (3) 2 1 17 (4) (3) 1 17 Typeset by AMS-LATEX