1 Cu S CuFeS Cu O Cu (OH ) CO 3 Ag S AgCl Cu (I) FeS,CuCO 3.Cu(OH),Cu (I) S ( ) ( ) 76.3% 6

1 Cu S CuFeS Cu O Cu (OH ) CO 3 Ag S AgCl Cu (I) FeS,CuCO 3.Cu(OH),Cu (I) S ( ) ( ) 76.3% 6

1 1 Cu Au (n-1)d 10 ns 1 1 3 1 1 3 IA IIA IB IIB s 1 IB IA

ds 18 IA IIA 8 3 Cu Au 4

1 ZnS ZnCO 3 ( )HgS 3 4

1 (n-1)d 10 ns (n-1)d p ( ) 1( [-Hg-Hg-] ) Zn-Cd-Hg Zn Cd

4 M 5 M 18 Zn Cd Hg Cd Hg 6

1 (1) Cu( ) Ag( ) Au( ) () 5 19.3g cm -3 (3) (4) Ag > Cu > Au (5) 1g 3.4km 0.0001mm (6)

1 3 (n 1)d ns 4s 3d 3s p 1

/(kj mol 1 ) 745.5 731.0 890.1 Cu Au Cu Au

1 O Cu O H O CO = Cu(OH) CuCO 3 H S Ag S Ag S H S M = Cu, Ag, Au 4M 4Cu O O H H O 8CN O 8NH 3 4[M(CN) 4[Cu(NH 3 ] ) ] 4OH ( ) OH O [Cu(NH ) ] 3 4 ( )

Cu Ag Au O 4H NO 3Cu(NO ) ) 8HNO ( 3Cu O H NO ) Cu(NO ) 4HNO ( Cu 3 3 3 3 O H NO ] H[AuCl ) ( HNO ) 4HCl( Au O H SO (s) SO Ag ) ( SO H Ag O H SO CuSO ) ( SO H Cu O H NO AgNO ) ( HNO Ag 4 3 4 4 4 4 3 3

Ag H S Ag S(s) H (g) Ag H 4I AgI - H (g) Cu H 4CS(NH ) Cu[CS(NH ) ] H (g) Cu 4 CN - H O = Cu(CN) 4 3- OH - 1/ H Cu 8 NH 3 O H O = [Cu(NH 3 ) 4 ] 4 OH - 3 Cu Ag Au Cl Cl Cl Cu > Ag > Au

1

B ( SO ) As O 3 Sb O 3 CuFeS O = Cu S FeS SO FeS 3O = FeO SO

173 K FeS FeO FeO SiO FeSiO 3 Cu S FeS 98% C FeSiO 3 Cu S FeS FeO SiO = FeSiO 3 ( ) mcu S nfes =

D Cu S 3O = Cu O SO Cu O Cu S = 6Cu SO E Cu( )- e - = Cu Cu e - = Cu ( 99.95%)

4 Ag 8 NaCN H O O = 4 Na[Ag(CN) ] 4 NaOH Ag S 4 NaCN = Na[Ag(CN) ] Na S [Ag(CN) ],, [Ag(CN) ] - Zn = Zn(CN) - 4 Ag

3 NaCN(0.03 0.% ) Au( Ag) Zn Al Au 4Au 8CN - O H O = 4[Au(CN) ] - 4OH - Au S 4CN - = [Au(CN) ] - S - [Au(CN) ] - Zn = Au [Au(CN) 4 ] -

3 Cu(I) 1 Cu O Cu O CuO 4 CuO = Cu O O Cu Cu O 4 Cu 8 OH - N H 4 = Cu O N 6 H O

Cu O [Cu(OH) 4 ] - CH OH(CHOH) 4 CHO = 4 OH - CH OH(CHOH) 4 COOH H O Cu O Cu C 4 H 4 O 6 Fehling( ) Cu O

Cu O Cu O Cu Cu Cu O H = Cu Cu H O Cu O 135 Cu O Cu O 4 NH 3 H O = [Cu(NH 3 ) ] OH - NaOH CuCl CuOH CuOH Cu O

CuCl CuBr CuI : Cu Cu 4 Cl - = [CuCl ] - ( ) Cu 4 I - = CuI I CuCl [Cu(NH 3 ) ] [CuCl ] - [CuCl 3 ] - [CuCl 4 ] 3- Cu(I) CuCl 4CuCl O 4H O = 3CuO CuCl 3 H O HCl Cu(I) CuI( ) Hg = Hg I ( ) Cu

3 Cu S S Cu(I) H S Cu S Cu O S - O - S - Cu(I) Cu S ( ) 3 Cu S 16 HNO 3 = 6 Cu(NO 3 ) 3 S 4 NO 8 H O Cu S 4 CN - = [Cu(CN) ] - S -

4 Cu 3 4 Cu d 10 d d [Cu(NH 3 ) ] [Cu(NH 3 ) 4 ] O 4 [Cu(NH 3 ) ] O 8 NH 3 H O = 4 [Cu(NH 3 ) 4 ] 4 OH - Cu(I) CO [Cu(NH 3 ) ]Ac CO C H 4 [Cu(NH 3 ) ] CO = [Cu(NH 3 ) (CO)] [Cu(NH CH CH OH) ] C H 4 = [Cu(NH CH CH OH) (C H 4 )]

Cu(II) 1 CuO Cu(NO 3 ) = CuO 4 NO O Cu O = CuO CuO CuO H = Cu H O CuO 1000 4 CuO = Cu O O CuO

Cu(OH) Cu(OH) = CuO H O T = 353 ~ 363 K H NH 4 Cu(OH) NH 3 H O NH 4 = [Cu(NH 3 ) 4 ] 4 H O Cu(OH) 4 NH 3 H O H = [Cu(NH 3 ) 4 ] 6 H O Cu(OH) H SO 4 = CuSO 4 H O Cu(OH) NaOH = Na [Cu(OH) 4 ]

CuF CuCl CuBr CuF H O CuCl H O CuCl Cu 4 Cl : CuCl CuCl CuCl - 4 [Cu(H O) 4 ]Cl CuCl CuCl

3 CuSO 4 O S O O S O O H O Cu H O H O O H O Cu H O H O O H O H O O H O [Cu(H O) 4 ]SO 4 H O

4 Cu(II) Cu(II) 4

Cu HN(CONH ) (NH CONHCONH ) NaOH CuSO 4

Cu(I) Cu(II) 1 Cu(I) < Cu(II) Cu O HSO 4 CuSO 4 Cu HO Cu 0.15 Cu 0.51 Cu E θ ( ) > E θ ( ) Cu Cu Cu Cu K θ =1.0 10 6

Cu(I) Cu O HCl CuCl(s) HO

3 Cu(I) > Cu(II)

1 1 Ag O Ag AgOH AgOH Ag O - Ag OH AgO(s, ) H O

Ag O Cu O Ag O Cu O Ag O 300 AgO Cu O Ag O HNO 3 Ag(I) Ag O HNO 3 = AgNO 3 H O Cu O Cu(I) Cu Cu Ag O [Ag(NH 3 ) ] Ag O 4 NH 3 H O = [Ag(NH 3 ) ] OH - Cu O

AgX AgF Ag O AgBr = Ag Br AgBr NaS O 3 AgBr AgBr S O 3 - = [Ag(S O 3 ) ] 3- Br -

3 Ag [Cu(NH 3 ) ] [Ag(NH 3 ) ] [Ag(S O 3 ) ] 3- [Ag(NH 3 ) ] : [Ag(NH 3 ) ] RCHO 3OH - = Ag RCOO - 4NH 3 H

3 473 K AuCl 3 AuCl 3 [AuCl 4 ] Br [AuBr 4 ] - I AuI 3 Au(I) Au(III) : 3Au = Au 3 Au

4 1 IIA IB Zn 419 o C : ZnS ZnO ZnCO 3 Cd 31 o C Hg -39 o C HgS Cu-Zn Ag-Hg Na-Hg Au-Hg

1 O 4Zn O CO 3H O = ZnCO3 3Zn(OH) Zn O Cd O 360 o C 470 o C ZnO(s, ) CdO(s, ) Hg O HgO(s)

S MS MS ZnS( ) CdS( ) HgS( ) ( ) Hg Zn Cd Hg Cd Hg

Hg Hg (195 Minimata Hg 5 Hg CH 3 HgCH 3, ) Hg Hg Hg

3 O 4H NO ) (NO 3Hg ) ( 8HNO ) 6Hg( O 4H NO ) 3Hg(NO ), ( 8HNO 3Hg O H NO ) Hg(NO ) ( 4HNO Hg O H SO HgSO ) ( SO H Hg Zn,Cd) (M H M ) ( H M 3 3 3 3 3 3 4 4 = OH H ) Zn(NH O H 4NH Zn H Zn(OH) O H OH Zn 4 3 3-4 4 OH - NH 3

( 1

3 Fe CaO Hg HgS Fe = Hg FeS HgS 600 700 HgS O = Hg SO 4 HgS 4 CaO = 4 Hg 3 CaS CaSO 4

5 (II) d d 1 Zn Cd Zn Cd Cd = Cd Cd CdO ZnO

1 (ZnO) (Zn(OH) ): Zn(OH) Zn(OH) Zn(OH) OH - = [Zn(OH) 4 ] - Zn(OH) 4NH 3 = [Zn(NH 3 ) 4 ] OH - ZnO Zn(OH) Δ ZnO(s, ) HO

700 ZnCl Zn Zn H O = Zn(OH) H ZnCl H[ZnCl (OH)] ( 6M ZnCl ph=1 ) ZnCl H O H[ZnCl (OH)] Fe O 3 6H[ZnCl (OH)] Fe[ZnCl (OH)] 3 3H O ZnCl ZnCl SOCl ZnCl xh O xsocl ZnCl xhcl xso

3 Zn H S ZnS ( ) H ZnS BaSO 4 ZnS BaSO 4 ( ) ZnS H S ZnS ZnS Cu Mn Ag

4 Zn Zn Zn 4NH 3 = [Zn(NH 3 ) 4 ] Zn 4CN - = [Zn(CN) 4 ] - [Zn(CN) 4 ] - [Cu(CN) 4 ] 3- (Cu-Zn [Cu(CN) 4 ] 3- e - = Cu 4CN -, E θ = -1.7 V [Zn(CN) 4 ] - e - = Zn 4CN -, E θ = -1.34 V Zn Cu

6 Cd Cd Cd(OH) OH NH - 3 H NH 4 O Cd(OH) NH 3 Cd(OH) NH Cd(NH 3 ) 4 4 H O Cd d 10 Cd(OH) Cd(OH) Δ CdO(s, ) HO 7 Cd H S Cd CdS(s, ) 6mol L -1 HCl

8 1 M(I) Hg(I) (HgO) 500 HgO Hg(OH) HgO Hg OH - HgO ( ) H O Hg(NO 3 ) = HgO ( ) 4NO O HgO

9 HgCl ) Cl Hg Cl HgCl 80, HgCl HgCl HgCl HgCl HgCl HgCl H O = Hg(OH)Cl HCl HgCl HgCl NH 3 Hg(NH )Cl ( ) NH 4 Cl

HgCl [HgCl 4 ] - HgCl : HgCl Cl - [HgCl 4 ] - E θ (HgCl /Hg Cl )=0.63V E θ (Sn 4 /Sn )=0.154V E θ (Hg Cl /Hg )=0.68V HgCl SnCl Hg Cl HgCl SnCl Hg Cl SnCl 4 SnCl Hg Cl, Hg Cl SnCl Hg SnCl 4 Hg( ) Sn( ) HgCl HgCl

(Hg Cl ): HgCl Hg Cl : HgCl Hg Hg Cl Hg Cl (Cl-Hg-Hg-Cl) Hg Cl HgCl Hg Hg Cl Hg Cl NH 3 Hg(NH )Cl ( ) Hg ( ) NH 4 Cl Hg(I)

Hg Cl HgCl Hg 5d 10 6s HgCl,, 5d 10 6s Cl Hg Hg Cl {Hg-Hg}, Hg X-

10 [Hg(NO 3 ) ] [Hg (NO 3 ) ] Hg(NO 3 ) H O HgO Hg(NO 3 ) HNO 3 Hg (NO 3 ) H O Hg (OH)NO 3 HNO 3 Hg(NO 3 ) Hg (NO 3 )

KI Hg(NO 3 ) KI HgI KI [HgI 4 ] - Hg I - HgI HgI I - [HgI 4 ] - Hg (NO 3 ) KI Hg I KI [HgI 4 ] - Hg I - Hg I Hg I I - [HgI 4 ] - Hg NH 3 Hg (NO 3 )

Hg SCN Hg(SCN) - SCN - Hg(SCN) (s) Hg(SCN) - 4 (aq, ) Hg (NO 3 ) HgO NO

E θ (Hg /Hg )=0.911V E θ (O /H O)=1.9V

6 1 OH - Hg Hg OH 400 C HgO(s, ) Hg(s) OH Hg O(s, ) HgO(s) Hg 1 O S - Hg Hg S S - HgS(s, ) HgS Hg

3 Hg Hg(NO 3 ) 3Hg Hg(NO 3 NO ) - 3 S HgS S - Hg(NO 3HgS(s, ) 3 ) HgS(s, ) NO - 3 3HgS HNO 3 1HCl 3H [HgCl 4 ] NO 3S 4H O HgS S - HgS - 4 [HgI 4 ] - HgI - 4 Nessler NH NH 4 [HgI 4 ] - 4OH - 4 Hg = O Hg : HN I(s) 7I - 3H O

Hg(I) Hg(II) Hg (aq) = Hg(l) Hg (aq) Hg Hg OH - NH 3 S - CO - 3 I -, CN - Hg OH - HgO Hg H O Hg H S HgS Hg H Hg 4 I - HgI 4 - Hg

Hg (I) Hg (II) Hg (l) 1. Hg Cl NH 3 H O H N-Hg-ClHg(l) NH 4 Cl H O Hg. Hg H S = Hg S H ( ) Hg S HgS Hg(l) 3. Hg Cl I - = Hg I Cl - Hg I I - ( ) = [HgI 4 ] - Hg (l) Hg Cl 4I - = [HgI 4 ] - Hg (l) Cl - K = 6.8 10 9