[Co(NH 3 ) 6 ] 3 [PtCl 4 ] 2 [SiF 6 ] 2 [Cu(H 2 O) 6 ] 2 [Cu(NH 3 ) 4 ] 2 [Co(NH 3 ) 6 ]Cl 3 K 4 [Fe(CN) 6 ][Cu(NH 3 ) 4 ]SO 4 F Cl Br I O OH S 2 CN H 2 O NH 3 KCl MgCl 2 KMgCl 3 (KClMgCl 2 ) 2 KCl PtCl 2 K 2 [PtCl 4 ] (NH 4 ) 2 Cu(SO 4 ) 2 6H 2 O CuSO 4 5H 2 O + (NH 4 ) 2 SO 4 + H 2 O (NH 4 ) 2 Cu(SO 4 ) 2 6H 2 O

QSS QQS QS 2016.2 g / 100 g2517.9 g / 100 g6024.0 g / 100 g CuSO 4 5H 2 O 249.7 CuSO 4 159.6 (NH 4 ) 2 SO 4 132.2 (NH 4 ) 2 Cu(SO 4 ) 2 6H 2 O 399.9 (NH 4 ) 2 Cu(SO 4 ) 2 291.9 CuSO 4 5H 2 O12.5 g (0.050 mol)h 2 O25 cm 3 (NH 4 ) 2 SO 4 6.6 g (0.050 mol) CuSO 4 5H 2 O H 2 O [Cu(H 2 O) 6 ] 2 2 SO 4 [Cu(H 2 O) 6 ] 2 4 NH 3 [Cu(NH 3 ) 4 ] 2 6 H 2 O CuSO 4 5H 2 O 4 NH 3 [Cu(NH 3 ) 4 ]SO 4 H 2 O 4 H 2 O CuSO 4 5H 2 O SO 2 4 SO 2 4 SO 2 4 H 2 O H 2 O 2 SO 4 [Cu(H 2 O) 6 ] 2

Cu 2+ [Cu(H 2 O) 6 ] 2 d e g t 2 Cu 2+ NH 3 H 2 O Cu 2+ H 2 O NH 3 z NH 3 H 2 O H 2 O [Cu(NH 3 ) 4 ] 2 Cu 2+ d d e g t 2g d e g I Br Cl F OH C 2 O 4 2 H 2 O-NCSpyNH 3 NO 2 CN H 2 O OH Cu(OH) 2 NH 3 [Cu(NH 3 ) 4 ]SO 4

6.3 g0.025 mol CuSO 4 5H

ph Brnsted Brnsted (acid) H (base) H H HA B HB A HA B HB A HA H 2 O H 3 O A B H 2 O HB OH B H 2 O HB OH H 2 O H 2 O H 3 O OH HA CH 3 COOHB PO 4 3 B NH 3 B NaOHKOH etc. NaOH Na OH a (H3O) a (OH) [H 3 O ][OH ] [H ][OH ] [H 3 O ][OH ]1.0010 7 mol dm 3

E = E 0 " RT nf ln a c C # a d D # ## a a A # a b B # ## E = E 0! RT F ln a Cl - E M = " RT nf { ln[ H+ ] "ln H + X } [ ] S E M = 2.303RT F { ph( X)"pH( S) } ( ) ph X = 1.984 "10 #4 T { ( )# ph( S) }

E M V = 0.0592{ ph( X) " ph( S) }

[ CH 3 COO " ][ H 3 O + ] K a = = CH 3 [ H COOH 3 O + ] # C S C A [ ] [ H 3 O + ]= K a! C A C S ph = pk a + log C S C A [ H 3 O + ] = K a " n A n S ph = pk a + log n S n A = pk a " log n A n S

K a = [ A - ] H 3 O + [ ] [ HA] [ ] [ A - ] [ K b = HA] OH" [ H 3 O + ] = K W K b " n S n B = K a " n S n B ph = pk a + log n B = pk n a "log n S = ( pk S n W " pk b )" log n S B n B

I di l " = #k I 0 " c dl log I = "k I 0 I 0 2.303 c l = "# c l A = log I 0 = " c l I

K a = H + [ ][ In - ] [ HIn] [ ] pk a = ph - log In- [ HIn] a

H + [ ] = 1 " # 2 C A + C 2 A + 4K W $ % & ' [ H + ] = C A 2 + K W (1) 2.0010 3 mol dm 3 (2) 1.0010 7 mol dm 3 (3) 1.2010 9 mol dm 3 OH " [ ] = 1 # 2 $ C B + C B % 2 & + 4K W ' ( poh OH " [ ] = C B 2 + K W

(1) 5.0010 2 mol dm 3 (2) 3.0010 7 mol dm 3 (3) 2.0010 9 mol dm 3 [ ][ A " ] K a = H+ [ HA] ([ ] "[ OH " ] ) ( [ ]) [ H + ] H + K a = C A " [ H + ]" OH " [ H + ] 2 K a = C A " H + [ ] [H ][H ] ph H { + K 2 a + 4K a C A " K a } [ ] = 1 2 12 C A >>[A ][H ][OH ] 15 K a = H+ [ ] ([ H + ] "[ OH " ] ) C A = # [ ]" K & W $ [ H + ( ] ' C A [ H + ] % H + H + [ ] = K a C A + K W H + [ ] = K a C A ph = 1 ( 2 pk a "logc A )

[ ][ OH " ] K b = BH+ [ B] [ ]( [ OH " ] "[ H + ] ) ( [ ] ) OH " K b = C B " [ OH " ]" H + [ ] 2 [ ] OH " K b = C B " OH " OH { " K 2 b + 4K b C B " K b } [ ] = 1 2 [ ]( [ OH " ] "[ H + ] ) K b = OH " # [ OH " ]% OH " $ = C B [ ] " K W [ OH " ] C B & ( ' [OH ]poh ph OH " [ ] = K b C B +K W OH " [ ] = K b C B

poh = 1 ( 2 pk b " logc B ) [ ] [ A " ] [ K b(a " ) = HA] OH " = K W K a (HA)

[ ] [ ] K a(bh + ) = K [ W = B] H+ K b( B) BH + [ H + ] = K a( HA) K a BH + ( ) = K a( HA) K W K b( B) [ ] ph = 1 " 2 pk a( HA) + pk % # $ a( BH + ) &' = 1 2 pk a( HA) ( pk b( B) + pk W

E = E 0 " RT nf ln a Red a Ox l

E = E 0 " 0.059V 5 [ ] Mn2+ log - [ MnO 4 ] KMnO 4 b 2 cm 3 C 2 O 4 2 fo fr fo

foa fr foa KMnO 4 (COONa) 2

complex Komplex Verbindung Diesbach Prussian BlueKFe II Fe III (CN) 6 Tassaert CoCl 3 6NH 3 complex salt Berzelius Blomstrand CoCl 3 6NH 3 Jorgensen Cl - CoCl 3 6NH 3 [Co(NH 3 ) 6 ]Cl 3 CoCl 3 5NH 3 [CoCl(NH 3 ) 5 ]Cl 2 CoCl 3 5NH 3 H 2 O [Co(H 2 O)(NH 3 ) 6 ]Cl 3 CoCl 3 4NH 3 trans-[cocl 2 (NH 3 ) 4 ]Cl CoCl 3 4NH 3 cis-[cocl 2 (NH 3 ) 4 ]Cl 24

Blomstrand-Jorgensen Werner Alfred Werner Werner MA 6 CoX 3 6NH 3 MA 4 PtX 2 4NH 3 X MA 6 MA 4 25

Hauptvalenz Nebenvalenz 26

d xy E d d xz d yz d x 2!y 2 t 2 g d z 2 d Ti 4+ [TiF 6 ] 2- e g 0.6D o D o 0.4D o t 2g e g 27

International Union of Pure and Applied Chemistry; IUPAC IUPAC [CoBrCl(H 2 O) 2 (NH 3 ) 2 ] [PtCl 2 (NH 3 ) 2 ] -ate ide -ite,ate K 4 [Fe(CN) 6 ] [Co(NH 3 ) 6 ]Cl 3 [CoCl(NH 3 ) 5 ]SO 4 NH 3 H 2 O CO NO ide, -ite, -ate ido, ito, -ato o F fluoro NO - 3 nitrato Cl - chloro NO - 2 nitro OH - hydroxo) SCN - thiocyanato CN - cyano H - hydrido) CH 3 COO - acetato 2- CO 3 carbonato 28

SCN - NO 2 - M-SCN M-NO 2 M-NCS M-ONO!", # µ µµ 29

２ 無機塩の溶解度 30

Cu 2+ + NH 3 [Cu(NH 3 )] 2+ [Cu(NH 3 )] 2+ + NH 3 [Cu(NH 3 ) 2 ] 2+ [Cu(NH 3 ) 2 ] 2+ + NH 3 [Cu(NH 3 ) 3 ] 2+ [Cu(NH 3 ) 3 ] 2+ + NH 3 [Cu(NH 3 ) 4 ] 2+! 4 = [Cu(NH 3) 4 2+ ] [Cu 2+ ][NH 3 ] 4 Cu 2+ + 4NH 3 [Cu(NH 3 ) 4 ] 2+ K 1 = [Cu(NH 3) 2 + ] [Cu 2+ ][NH 3 ] [Cu(NH K 2 = 3 ) 2+ 2 ] [Cu(NH 3 ) 2+ ][NH 3 ] K 3 = K 4 = [Cu(NH 3 ) 3 2+ ] [Cu(NH 3 ) 2 2+ ][NH 3 ] [Cu(NH 3 ) 4 2+ ] [Cu(NH 3 ) 3 2+ ][NH 3 ]! 4 = [Cu(NH 3 ) 4 2+ ] [Cu 2+ ][NH 3 ] 4 = [Cu(NH 3) 2+ ] [Cu 2+ ][NH 3 ]! [Cu(NH 3 ) 2+ 2 2 ] [Cu(NH 3 ) 2+ ][NH 3 ]! [Cu(NH 3 ) + 3 ] [Cu(NH 3 ) 2+ 2 ][NH 3 ]! [Cu(NH 3 ) 2+ 4 ] [Cu(NH 3 ) 2+ 3 ][NH 3 ] = K 1 K 2 K 3 K 4 log[nh 3 ] free {[Cu(NH 3 ) x ] 2+ } 31

4 吸収スペクトルと構造 ph 指示薬の pka と変色 吸収スペクト 32

I K a pk a Ka pka H 2 O 2 2.410 12 11.62 H 3 BO 3 (K a1 ) 5.810 10 (pk a1 ) 9.24 H 2 BO 3 (K a2 ) 110 14 (pk a2 ) 14 H 2 CO 3 (K a1 ) 4.510 7 (pk a1 ) 6.35 HCO 3 (K a2 ) 4.710 11 (pk a2 ) 10.33 HCN 6.210 10 9.21 HNO 2 5.610 4 3.25 HNO 3 (25) (-1.4) HF 6.310 4 3.20 H 3 PO 4 (K a1 ) 6.910 3 (pk a1 ) 2.16 H 2 PO 4 (K a2 ) 6.210 8 (pk a2 ) 7.21 2 HPO 4 (K a3 ) 4.810 13 (pk a3 ) 12.32 H 2 S (K a1 ) 8.910 8 (pk a1 ) 7.05 HS (K a2 ) 110 19 (pk a2 ) 19 H 2 SO 3 (K a1 ) 1.410 2 (pk a1 ) 1.85 HSO 3 (K a2 ) 6.510 8 (pk a2 ) 7.19 H 2 SO 4 (K a1 ) (10 3 ) (pk a1 ) (-3) HSO 4 (K a2 ) 1.010 2 (pk a2 ) 1.99 HSCN (63) -1.8 HCl (10 8 ) (-8) HClO 4.010 8 7.40 HClO 2 1.110 2 1.94 HClO 3 (10) (-1) H 2 CrO 4 (K a1 ) 1.810 1 (pk a1 ) 0.74 HCrO 4 (K a2 ) 3.210 7 (pk a2 ) 6.49 HBr (10 9 ) (-9) HI (10 10 ) (-10) NH 2 SO 3 H 8.910 2 1.05 HCOOH 2.810 4 3.55 CH 3 COOH 2.810 5 4.56 CH 2 ClCOOH 2.110 3 2.68 H 2 C 2 O 4 (K a1 ) 9.110 2 (pk a1 ) 1.04 HC 2 O 4 (K a2 ) 1.510 4 (pk a2 ) 3.82 H 2 C 4 H 4 O 6 (K a1 ) 1.510 3 (pk a1 ) 2.82 HC 4 H 4 O 6 (K a2 ) 1.110 4 (pk a2 ) 3.96 [CH 2 N(CH 2 COOH) 2 ] 2 (K a1 ) 3.210 2 (pk a1 ) 1.5 (H 4 EDTA) H 3 EDTA (K a2 ) 1.010 2 (pk a2 ) 2.0 H 2 EDTA 2 (K a3 ) 2.110 3 (pk a3 ) 2.68 HEDTA 3 (K a4 ) 7.810 7 (pk a4 ) 6.11 (a) D. R. Lide(Editor-in-Chief), CRC Handbook of Chemistry and Physics, 77th Edition, CRC Press, Boca Raton, 1996. (b) 1993 33

II pk(20) 0.01.6 1.3 0.21.8 0.41.8 1.65 1.22.8 m - 1.5 1.22.8 2, 4-2.04.7 3.2 2.94.0 4.10 3.04.6 3.05.0 3.44 * 3.24.4 4.90 3.85.4 5.00 4.86.0 4.58.3 p - 5.46.6 6.25 5.26.8 6.20 * 5.26.8 7.20 * 6.07.6 8.04 * 6.68.0 7.4 6.88.0 m - 8.35 6.88.6 8.46 7.08.8 m - 8.3 7.49.0 9.23* 8.09.6 9.5 8.010.0 o - 8.29.8 9.410.6 10.112.0 O 11.013.0 11.614 2,4,6-11.513.0 1,3,5-12.014.0 * 25 (a) D. R. Lide(Editor-in-Chief), CRC Handbook of Chemistry and Physics, 77th Edition, CRC Press, Boca Raton, 1996. (b) 1993 34

III E o 25* E o / V Ag / Ag Ag + e Ag(s) 0.800 AgCl / Ag AgCl(s) + e Ag(s) + Cl 0.222 Al 3 / Al Al 3 + 3e Al(s) 1.662 H 3 AsO 4 / H 3 AsO 3 H 3 AsO 4 + 2H + 2e H 3 AsO 3 + H 2 O 0.560 H 3 AsO 3 / As H 3 AsO 3 + 3H + 3e As(s) + 2H 2 O 0.248 Au / Au Au + e Au(s) 1.692 Ba 2 / Ba Ba 2 + 2e Ba(s) 2.912 Be 2 / Be Be 2 + 2e Be(s) 1.847 BiO / Bi BiO + 2H + 3e Bi(s) + H 2 O 0.320 BiOCl / Bi BiOCl + 2H + 3e Bi(s) + Cl +H 2 O 0.158 Br 2 / Br Br 2 (aq) + 2e 2Br 1.087 CO 2 / H 2 C 2 O 4 2CO 2 + 2H + 2e H 2 C 2 O 4 0.475 Ca 2 / Ca Ca 2 + 2e Ca(s) 2.868 Cd 2 / Cd Cd 2 + 2e Cd(s) 0.403 HClO / Cl HClO + H + 2e Cl + H 2 O 1.482 Cl 2 / Cl Cl 2 (g) + e 2Cl 1.358 Ce 4 / Ce 3 Ce 4 + e Ce 3 1.72 Co 3 / Co 2 Co 3 + e Co 2 1.92 Co 2 / Co Co 2 + 2e Co(s) 0.28 2 Cr 2 O 7 / Cr 3 2 Cr 2 O 7 + 14H + 6e 2Cr 3 + 7H 2 O 1.232 2 CrO 4 / Cr(OH) 3 2 CrO 4 + 4H 2 O + 3e Cr(OH) 3 (s) + 5OH 0.13 Cr 3 / Cr Cr 3 + 3e Cr(s) 0.744 Cs / Cs Cs + e Cs(s) 3.026 Cu 2 / Cu Cu 2 + 2e Cu(s) 0.342 Cu 2 / Cu Cu 2 + e Cu 0.153 Cu / Cu Cu + e Cu(s) 0.521 F 2 / F F 2 (g) + 2e 2F 2.866 Fe 3 / Fe 2 Fe 3 + e Fe 2 0.771 Fe 2 / Fe Fe 2 + 2e Fe(s) 0.447 Fe(OH) 3 / Fe(OH) 2 Fe(OH) 3 (s) + e Fe(OH) 2 (s) 0.56 3 Fe(CN) 6 4 / Fe(CN) 6 3 Fe(CN) 6 + e 4 Fe(CN) 6 0.358 H / H 2 2H + 2e H 2 (g) 0.000 Hg 2 / Hg Hg 2 + 2e Hg(l) 0.851 Hg 2 2 / Hg 2 2Hg 2 + 2e Hg 22 0.920 2 2 Hg 2 / Hg Hg 2 + 2e 2Hg(l) 0.797 35

III () E o / V SbO / Sb SbO + 2H + 3e Sb(s) + 2H 2 O 0.212 Hg 2 Cl 2 / Hg Hg 2 Cl 2 (s) + 2e 2Hg(l) + 2Cl 0.268 I 2 / I I 2 (s) + e 2I 0.536 K / K K + e K(s) 2.931 Li / Li Li + e Li(s) 3.040 Mg 2 / Mg Mg 2 MnO 4 MnO 4 / Mn 2 MnO 4 / MnO 2 MnO 4 + 2e Mg(s) 2.372 + 8H + 5e Mn 2 + 4H 2 O 1.507 + 2H 2 O + 3e MnO 2 (s) + 4OH 0.595 MnO 2 / Mn 2 MnO 2 (s) + 4H + 2e Mn 2 + 2H 2 O 1.232 Mn 2 / Mn Mn 2 + 2e Mn(s) 1.185 NO 3 / NO NO 3 + 4H + 3e NO + 2H 2 O 0.957 NO / N 2 O 2NO + 2H + 2e N 2 O + H 2 O 1.591 NH 2 OH / N 2 H 4 2NH 2 OH(aq) + 2e N 2 H 4 (aq) + 2OH 0.73 N 2 H 4 / NH 3 N 2 H 4 (aq) + 2H 2 O + 2e 2NH 3 (aq) + 2OH 0.1 Na / Na Na + e Na(s) 2.714 Ni 2 / Ni Ni 2 + 2e Ni(s) 0.257 O 3 / O 2 O 3 (g) + 2H + 2e O 2 (g) + H 2 O 2.076 O 2 / H 2 O O 2 (g) + 4H + 4e 2H 2 O 1.224 O 2 / OH O 2 (g) + 2H 2 O + 4e 4OH 0.401 O 2 / H 2 O 2 O 2 (g) + 2H + 2e H 2 O 2 0.695 H 2 O 2 / H 2 O H 2 O 2 + 2H + 2e 2H 2 O 1.776 H 2 O / H 2 2H 2 O + 2e H 2 (g) + 2OH 0.828 Pb 2 / Pb Pb 2 + 2e Pb(s) 0.126 PbSO 4 / Pb PbSO 4 + 2e Pb(s) + SO 42 0.359 Rb / Rb Rb + e Rb(s) 2.924 SO 4 2 / H 2 SO 3 SO 4 2 + 4H + 2e H 2 SO 3 + H 2 O 0.172 H 2 SO 3 / S H 2 SO 3 + 4H + 4e S(s) + 3H 2 O 0.449 H 2 SO 3 / S 2 O 3 2 SO 3 2 / S 2 O 4 2 2H 2 SO 3 + 2H + 4e S 2 O 3 2 2SO 3 2 + 2H 2 O + 2e S 2 O 4 2 + 3H 2 O 0.40 + 4OH 1.12 S / H 2 S S(s) + 2H + 2e H 2 S(aq) 0.142 S / S 2 S(s) + 2e S 2 0.476 SbO / Sb SbO + 2H + 3e Sb(s) + 2H 2 O 0.212 Sn 4 / Sn 2 Sn 4 + 2e Sn 2 0.151 Sn 2 / Sn Sn 2 + 2e Sn(s) 0.138 Sr 2 / Sr Sr 2 + 2e Sr(s) 2.899 Zn 2 / Zn Zn 2 + 2e Zn(s) 0.762 36