InorganicChemistry英文PPT (37).ppt

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1、AgThe influence of the formation of precipitation on electrode potential)108.1)AgCl(V,799.0Ag)/(Ag 10sp-+=KEKnown thatExample:If NaCl is added to the half cell of Ag+/Ag solution,AgCl will be produced.When c(Cl-)=1.0 mol L-1,E(Ag+/Ag)=?0.222V=108.1lgV0592.00.799V10+=-)Ag/Ag(+E)aq(Cl)aq(Ag(s)AgCl+-+S

2、olution:Ag(s)e)aq(Ag+-+(AgCl)Cl()Ag(sp=-+Kcc(AgCl)Ag(,Lmol0.1)Cl(sp1=+-IfKcc)Ag(lgV0592.0)Ag/Ag(+=+cEAgCl)(lgV0592.0)Ag/Ag(sp+=+KE ,When NaOH is added into the half cell of ,when equilibrium is reached,keep?)FeFe(,Lmol0.1)OH(231=+-Ec,108.2)(OH)Fe(393sp=-K V769.0)FeFe(23=+,Known thatExample:E 1086.4)

3、(OH)Fe(172sp=-KFeFe23+Solution:,L1.0mol)OH(1Whenc=-)aq(3OH)aq(Fe (s)(OH)Fe33+-+)aq(2OH)aq(Fe (s)(OH)Fe22+-+)(OH)(Fe)(Fe 3sp3Kc=+)(OH)(Fe)(Fe 2sp2Kc=+V55.0 -=391086.4108.2lgV0592.0V769.017+=-)Fe/Fe(23+E)aq(Fe e)aq(Fe23+-+)(Fe)(Fe lgV0592.0)Fe/Fe(2323+=+ccE)Fe(OH)()Fe(OH)(lgV0592.0)Fe/Fe(2sp3sp23+=+KK

4、E?)/CuCu(L1.0mol)Cu(NH(21243=+-+,Ec,L1.0mol)NH(13=-WhencCuAmmonia water Influence of complex formation on electrode potential,0.3394V)/CuCu(2=+Known thatExample:E 1030.2)Cu(NH(12243f=+K ,In the half cell of /Cu,add ammonia,Solution:Lmol01)Cu(NH()NH(12433-+=When.c c)aq()Cu(NH )aq(4NH)aq(Cu24332+2+)NH

5、()Cu()Cu(NH(f43243+=Kccc )Cu(NH(1)Cu(243f2+=Kc0.0265V-=1030.21lg2V0592.00.3394V12+=)Cu/Cu(2+E)Cu(lg2V0592.0)Cu/Cu(22+=+cE)s(Cu 2e)aq(Cu 2+-+)Cu(NH(1lg20592V.0)Cu/Cu(243f2+=+KESolution:23)aq(Fe e(aq)Fe+-+363)aq(Fe(CN)aq(6CN(aq)Fe -+633636f/)CN(/)Fe(/)Fe(CN)()Fe(CN)(ccccccK-+-=Example:When KCN(s)is ad

6、ded to solutions containing 1.0 mol L-1Fe3+and 1.0mol L-1Fe2+,Fe(CN)63-and Fe(CN)64-ligand ions are generated.When c(CN-)=1.0mol L-1,cFe(CN)63-=cFe(CN)64-=1.0mol L-1 in the system,to calculate E(Fe3+/Fe2+)After adding KCN,The following coordination reaction occursLmol0.1)Fe(CN)()Fe(CN)()CN(14636-=Wh

7、enccc)aq(Fe(CN)aq(6CN(aq)Fe462-+/)CN(/)Fe(/)Fe(CN)()Fe(CN)(624646f-+-=ccccccK/)Fe(/)Fe(lgV0592.0)/FeFe()/FeFe(322323+-=ccccZEE)Fe(CN)(1/)Fe(36f3-+=Kcc)Fe(CN)(1/)Fe(46f2-+=Kcc0.36V=102.4104.1Vlg0592.00.769V4552-=)/FeFe(23+So,E)Fe(CN)()Fe(CN)(lgV0592.0)/FeFe(46f36f23-+-=KKZE9.Maximum work of galvanic

8、cell and Gibbs functionEMF-electromotive force(V)F-faraday constant 96485(C mol-1)Z-The amount of electron transferred in the battery reactionElectric work(J)=electric quantity(c)potential difference(V)Battery reaction:Standard state:MFmrZFEG-=DExample:To calculate the standard Gibbs function variat

9、ion of a galvanic cell composed of a standard hydrogen electrode and a standard cadmium electrode.(E =0.4030v)Battery symbol:(-)Cd|Cd2+(1.0moldm-3)H+(1.0moldm-)|H2(100kPa)|Pt(+)Solution:Battery reaction:Cd(s)+2H+(aq)=Cd2+(aq)+H2(g)In reaction n=2 G =-zFE =-296485Cmol-1 0.4030v =-77770Jmol-1=-77.77kJmol-1

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