無機(jī)化學(xué)課件27copperzinc40

1、Copper (Cu)Electron configuration: 4s13d103d103d93d8Properties Malleable and ductile; reddish. Good conductor of heat and electricity. Main oxidation state: IIOres: Cuprite: Cu2O Bornite Cu6FeS4 Azurite: Cu3(CO3)2(OH)2 Covellite: CuSUses Electrical wires and switches, plumbing, cooking vessels. Used

2、 as an alloy: brass (Cu/Zn), Bronze (Cu/Sn), Coinage material (Cu/Ni). Copper sulphate is used widely as an agricultural poison and as an algicide in water purification.Halides anhydrous fluoride CuF2 is white, the chloride yellow and the bromide almost black CuICopper(I) oxide, Cu2Oorange-yellow pr

3、ecipitateCopper(I) chloride, CuCl white solid, insoluble in water.Vapor state : dimer of formula Cu2Cl2concentrated hydrochloric acidProperties of CuCl The solid readily dissolves chemically in concentrated hydrochloric acid, forming a complex, and in ammonia as the colorless, linear, complex cation

4、 H3N Cu NH3+ ammoniacal copper(I) chloride is a good absorber for carbon monoxide, forming CuCl . CO . H2O, and as such is used in gas analysis.explosive when drynot in excess)Copper(l) chloride, bromide and cyanide were used by Sandmeyerto introduce a chlorine, a bromine atom and a cyanide groupres

5、pectively into a benzene ring by addition to the phenyl diazoniumsalt.TESTS FOR COPPER COMPOUNDS to add hexacyanoferrate(II) (usually as the potassium salt) when a chocolate-brown precipitate of copper(II) hexacyanoferrate(II) is obtained:chocolate-brownInert and Labile Complexes Complexes in which

6、ligands are rapidly replaced by others are called labile complexes (shorter than 1 min; 25 oC, 0.1M) Slow - inert complexesLabile complexes All complexes in which the central metal atom contains electrons in eg orbitals Ga(C2O4)33-, d10;Cu(H2O)62+, d9 Co(NH3)62+,d7Ni(H2O)62+,d8 Fe(H2O)63+, d5 All co

7、mplexes that contain less than three d-electrons Ti(H2O)63+, d1;V(phen)33+, d2 CaEDTA2-, d0Inert Complexes Octahedral d3 complexes, plus low spin d4, d5 and d6 systems Cr(H2O)63+,d3 Fe(CN)63-,d5 Co(NO2)63-,d6 PtCl62-,d6Why? Comparison of the CFSE of a coordination compound and of its activated compl

8、ex If the CFSE of the compound is much larger than that of the activated complex, the compound will react slowly Small fastCu Ag AuReaction with O222CuO2CuO() BlackAu，Ag O2 no reaction，But if forming precipitate or coordination compound, reaction can happen。2222232CuOH OCO Cu (OH) CO () greenAuAg,Cu

9、,M 23 4Cu(NH ) ()blueCan not use Cu as NH3 container。O2HS2AgOS2H2Ag2222O2Silverware tarnishes。2233 24CuO2H O8NH 4Cu(NH ) ()4OH colorless4OH4M(CN)8CNO2HO4M222Cu,Ag,Au soluble in oxidizing acids。33 222Cu4HNO ( )Cu(NO )2NO2H O c342Au4HCl( )HNO ( ) HAuCl NO(g)2H O cc2424222Ag2H SO ( )Ag SO (s)SO2H O c24

10、422Cu2H SO ( )CuSOSO2H O c3322Ag2HNO ( )AgNONOH O cAg compounds：Mostly insolublesoluble：AgNO3, AgF, AgClO4insoluble：AgCl, AgBr, AgI, AgCN, AgSCN, Ag2S, Ag2CO3, Ag2CrO4。Low thermal stability （light, heat）I) Br,Cl,(X X21AgAgXO212AgC300OAgO2NO2AgC4402AgNO2h22223colorAgCl AgBr AgI Ag2O Ag2CrO4 Ag2Swhite

11、 pale yellow dark blood black yellow brown redAg(I) reactionSilvering mirror reaction：O2H4NH2AgHCOO 3OHHCHO)2Ag(NH23-23-222Ag2OHAg O(s,)H O brown-232322OH)2Ag(NHOH4NHOAg42232NHO(s)AgOH2NH2Ag OH4NH2AgOHC 2OHOHC)2Ag(NH237126-6126232H(s)CrO2AgOHOCr4Ag422-27223-2323 2Ag2S O (in )Ag(S O ) excess2-2322322

12、2AgS O ()Ag S O (s,)H O Ag S(s,) small amountwhiteblack-2423342CrO)2Ag(NH4NHCrOAg Identification of S2O32-：)S(s,AgSOH OH)(s,OSAg2422322bwRelative stability of Ag+ complexesAgAgCl23)Ag(NHAgBr(s)3232)OAg(SAgI(s)2 Ag(CN)S(s)Ag23 HNOHCl3NH-Br232OS-I2AgICN-2S-I7231067. 1)Ag(NH(K f133232109 . 2)OAg(S(K f2

13、021048. 2)Ag(CN)(K fIdentification of Ag+ 233)Ag(NHNH )AgCl(s,HClAg3234232332NHAgI(s)I)Ag(NH2NHAgCl(s)Cl2H)Ag(NHCl)Ag(NH2NHAgClHAgCl(s)HClAgAgCl(s,white)AgI(s,yellow)I-HNO3 Mercury differs from zinc and cadmium in a number of significant ways. It is used in thermometers, barometers, electrical conta

14、cts, and in some types of electrochemical cells. Mercury vapor is used in fluorescent lamps. Dental amalgam is an alloy of mercury, silver, and tin, and is used for dental restorations. Long-term exposure to mercury can present a serious health hazard. Mercury can react with and inactivate sulfur-co

15、ntaining enzymes.MercuryMercury - Hg Mercury is a heavy, silvery, liquid metal. Mercury occurs very rarely free in nature, but can be found in ores.Mercury easily forms alloys with other metals such as gold, silver and tin, which are called amalgams. Its ease in amalgamating with gold is made use of

16、 in recovering gold from its ores. The metal is widely used in making advertising signs, mercury switches, and other electrical apparatus. It is used in laboratory work for making thermometers, barometers, diffusion pumps and many other instruments. Other uses are in pesticides, dental work, batteri

17、es and catalysts.It is a virulent poison, readily absorbed through the respiratory tract, the gastrointestinal tract or through the skin. It is a cumulative poison and dangerous levels are readily attained in air. It is always handled with the utmost care.Mercury is stable with air and water. It is

18、a rather poor conductor of heat compared to other metals, and a fair conductor of electricity Reactions of Hg2. S2-2222-2HgSHgS(s,black)HgSHgSHg 1. OH-222221OH400 CHgHgO(s,yellow)Hg(s)O2HgHg O(s,brown)HgO(s)Hg If Hg2+ comes from Hg(NO3)2：2-233 22-3 233Hg2NO2SHg(NO )2HgS (s,yellow)Hg(NO )2HgS S3HgS(s

19、,black)2NO HgS -0.758V Hg2S -0.598V Hg-22-22423HgSSHgSO4H3S2NO HgCl3H12HCl2HNO3HgSHgS： =1.610-52KspTherefore：Hg(I) is stable in solution，but disproportionate when precipitate or complex forms。Aminomercuric chloride 3. Reaction with NH3In general, all these products are obtained in proportions which

20、depend on the concentrations of NH3 and NH4+ and on the temperature, but more or less pure products can be prepared by suitablyadjusting the conditionsHg(NH3)2Cl2, descriptively known as “fusible white precipitate”,the amide Hg(NH2)Cl, “infusible white precipitate”2-2332234 2HgNO4NHH O HgO NH HgNO (

21、s,white)2Hg3NH 2-332234HgNO4NHH O HgO NH HgNO (s,white) 3NH OHNO)2Hg(NH 4NH3NHHgNONHHgO2-32433432 )Hg(NH4NHHg24332adding will shift eq to right NH4-24NesslerHgI 4NHreagent， is-IHgHgI-24 reaction with I-，SCN-2-2)(s,HgI2IHg gold-24-2)(aq,HgI2IHgI colorless222-22HgHgI)(s,IHg2IHg green2-O3H7I 2-244)I(s,NH HgHg 4OH2HgINHbrownO22-2-2262-2-2262HgSn8ClHg Cl (s,white)SnClHg Cl (s)Sn4Cl2Hg(l,black)SnCl Can also use HgCl2 to identify Sn2+Identification of Hg2+)(aq,Hg(SCN)2SCNHg(SCN)-24-2colorless(s)Hg(SCN)2SCNHg