I B group elements, Cu,Ag,Au Physical Properties Property/Element Atomic radius(A) Density (g/cm3) Hardness(Mohs) m.p.(0C) b.p.

(0C) Standard electrod potential,E0(250,V) M+/M M2+/M+ M3+/M2+ Electrical conductivity (Hg=1) Thermal conductivity (Ag=1) Clark (%) O.S. C.N. Cu 1.28 8.98 2.5-3 1083 2310 +0.522 +0.345 55.6 0.94 7 x 10-2 I, II, III 4,6 Ag 1.44 10.54 2.5-2.7 960.5 1950 +0.799 +1.39 63.9 1.0 2 x 10-5 I, II, III 4,6 Au 1.50 19.43 2.5 1063 2600 +1.70 +1.50 38.5 0.75 5x10-7 I, II, III 4,6

IIB group elements, Zn,Cd,Hg Property/Element Atomic radius(A) Density (g/cm3) Hardness(Mohs) m.p.(0C) b.p.(0C) Standard electrod potential,E0(250,V) M2+/M Electrical conductivity (Hg=1) Thermal conductivity (Ag=1) Clark (%) O.S. Zn 1.38 7.14 2.5 419.4 907 +0.52 16.3 0.26 1.2 x 10-2 II Cd 1.54 8.64 2 320.9 767 +0.80 14.9 0.23 3x10-5 II Hg 1.57 13.56 -38.89 356.9 +1.70 1 0.02 4x10-5 II

Chemical Properties chemical reactivity decreases down the group Reactant Cu Wet air 2Cu + O2 + CO2+H2OCuCO3.Cu(OH)2 O2(air) CuO (t=2000C) black Cu2O(t=8000C)brown, orange S, H2S Cu2S, CuS (t=250C) X2 Conc. acids Acetic acid NH3 Aqua regia C CuX2 3Cu+8HNO33Cu(NO3)2+2NO+4H2O Cu +2H2SO4CuSO4 + SO2 + 2H2O Cu + 4HCl + O22CuCl2 + 2H2O 2Cu + 2CH3COOH + O2 Cu(CH3COO)2.Cu(OH)2 2Cu + 8NH3 + O2 + H2O 2[Cu(NH3)4](OH)2

Ag Ag2S (1800C) AgX reaction with HNO3,H2SO4 -

Au Au2S3black AuBr3 -

H[AuCl 4]

No direct reactions 2[M(NH3)2]NO3+C2H2M2C2+2NH4NO3+2NH3 M=Cu(I), Ag(I) Au + HNO3 + 4HCl H[AuCl4] + NO + 2H2O 2H[AuCl4] + 3H2S Au2S3 + 2HCl Stability of O.S. Cu(I) (d10) diamagnetic, colourless ; unstable state: disproportion : 2Cu+ Cu2+ + Cu Ag(I)- stable state diamagnetic, colouless Soluble salts : AgNO3, AgClO4,AgF Insoluble salts : Ag2SO4, AgCl Au(I) impure compounds : -mixtures of Au(I), Au(III), Au(0) disproportion : 6Au+ + 3H2O Au2O3 + 4Au + 6H+ Cu(II) (d9)paramagnetic,absorption,600-900 nm-blue-green Ag(II) unstable state, oxidant : AgF2,AgO Au(II) unknown Cu(III) (d8) few compounds Ag(III) few compounds : AgO(s) contains Ag(I) + Ag(III) Au(III)- characteristic state

Chemical properties- IIB group elements Zn is more reactive, Hg is different after H2 Reactant Zn Cd Wet air ZnO +ZnCO3.3Zn(OH)2 O2 ZnO CdO white white H2O(vap) M + H2O MO + H2 S,Se.Te MS,Mse,MTe Acids Nonoxidant: M + 2HCl MCl2 + H2 Oxidant M + 2H2SO4MSO4 + SO2 + 2H2O 3M + 8HNO33M(NO3)2 + 2NO +4H2O 4M + 10HNO34M(NO3)2+NH4NO3+3H2O Alkalies no Zn + KOH + 2H2O K[Zn(OH)3] + H2 NH3 no Zn + 4NH3 + 2H2O solution [Zn(NH3)4](OH)2+H2 N2 No direct reactions 3Zn + 2NH3Zn3N2 + 3H2 3M(NH2)2 Zn3N2 +9H2 + 2N2 (M=Zn,Cd,Hg) C No direct reactions M + C2H2 ZnC2 + H2 (M=Zn,Cd) ZnO + 3C ZnC2 + CO Hg2(NO3)2 + CaC2 Hg2C2 + Ca(NO3)2 Hg Hg2O,HgO yellow Only oxidant acids with

no no

Why all Hg(I) compounds are diamagnetic (as solids, in solutions) ? The majority of Hg(I) salts are colourless, insoluble Do you know two coloured salts?

Important uses of Cu,Ag and Au: Copper pure electrolyte -electrical wires and cables alloys -simple brasses (Cu + 45%Zn) tube for condensers,radiators clocks, watches -special brasses (Cu+Fe+Al+Sn+Si) ship-building -brass with high Cu content (tombac)similar Au decorative articles cheap jewelry -copper-nickel alloy- constantan thermocouples -bronzes (Cu + Sn) -machine-building

Silver, Gold Agno use in practice owing to its softness Alloys are used as -Ag-Cu jewelry,coins,laboratory utensils -Ag-Zn accumulators with good electrical characteristics and low mass and volume (K)- Ag2O (A) Zn (spongy) -Au- alloys Au-Ag electrical contacts, dentary technics, jewelry 24 carats-pure Au 18 carats- 75%Au,12.5%Ag+ 12.5%Cu white Au 80%Au + 15-20%Ni red Au 40-60% Au + 30-50% Cu + others : Ag,Ni,Zn

Silver saltsproduction of photografic materials-films,paper,glass Colloidal solutions of Ag (protargolum, collargolum)-stabilized with special additions disinfection of mucous membranes Uses of Zn, Cd, Hg: Zn- coatings (not effective in highly humid air,sea water) alloys brasses (Zn-Cu alloys) manufacture of galvanic dry cells (Zn MnO2 in a paste of NH4Cl) Cd -as rods in nuclear reactors for controlling the rate of the chain reaction (cd absorbss slow neutrons) -alkaline accumulators -alloysCu alloys with 1%Cd--for making telegraph, telephone, trolleybus wires (a greater strength and wear resistence than Cu) Hg cathode (production of NaOH, Cl2) catalyst organic synthesis -amalgams (Fe does not form an amalgam, Hg can be transpoted in steel vessels

Biochemistry of the elements Cu, Zn,Cd,Hg a variety of copper enzimes occur in plants and animals 3 types having : - distinctive geometries - different ligand environments - different O.S for copper Type Geometry of O.S. center Type I (blue Cu Distorted Td Cu(II) or enzimes): Trigonal Azurin bipyramid Plastocyanin Trigonal Cu(I) Laccase Absorption Electronassigned to carrier Cys(S)Cu2+ proteins (LMCT)

Ligands N and S

Type II Tyrosinase Ascorbate oxidase Oxygenation reactions Type III hemocyanin Oxygen transport

Trigonal Square planar 5-coordinated Oh distorted

Cu(I) Cu(II)

Square planar 5-coordinated Oh distorted

Binuclear Cu(II) Strong antiferomagnetic coupling

1970 Zn is crucial to DNA and RNA synthesis and to cell devision Metal center in Zinc-finger proteins- is a complex compound with Td coordination with two his and two cys Mercury vapour is very toxic and may cause serious poisoning Do not keep vessels with Hg open Demercurizers : - sulphur powder - 20% solution of FeCl3 - 10% solution of KMnO4 acidified with HCl

Cu, Ag, Au COMPOUNDS Oxides M2O (M=Cu,Ag) CuO + Cu Cu2O (brown) CuSO4 + 2NaOH Cu(OH)2 + Na2SO4 2Cu(OH)2 + C6H12O6 Cu2O + C6H12O7 + 2 H2O 2AgNO3 + 2NaOH Ag2O + 2NaNO3 + H2O Ag2CO3 Ag2O + CO2 covalent compounds with a great thermal stability, Ag2O (3000C) 2Ag + 1/2O2 insoluble in water, soluble in NH3 and in conc. acids: [Cu(NH3)2]OH, [CuX2]Cu2O + H2SO4 CuSO4 + Cu + H2O Ag2O + 2KCN + H2O 2K[Ag(CN)2] + 2KOH MO (M=Cu,Ag) black powders Cu(OH)2 CuO + H2O Cu(NO3)2 CuO + 2NO2 + 1/2O2 CuCO3 .Cu(OH)2 2CuO + CO2 + H2O Ag + O3 AgO + O2 (decomposes t>1000C) Au2O3 .nH2O HAuCl4 + 3NaOH Au (OH) 3 + 3NaCl + H2O + HCl Au(OH)3 (140-1500C) Au2O3 . n H2O by drying in air is obtained a yellow-brownish powder, Au2O3.nH2O ~HAuO2 amphoteric properties : Au(OH)3 + 4HCl H[AuCl4] + 3H2O Au(OH)3 + 4NaOH Na[AuO2] + 3H2O Give some examples of halides and oxosalts with knowing uses or with interesting structures AuCl3 , english green, Cu(CH3COO)2 . H2O