complexometric titration

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complexometric titration. 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 . 4.1 . 1 complex 2 coordination - PowerPoint PPT Presentation

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  • complexometric titration4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8

  • 4.1 1complex2coordination34

  • 1. ligand Cu2+NH3 Cu2++NH3 = CuNH32+ k1 =2.0104 CuNH32++NH3=CuNH322+ k2=4.7103

  • CuNH322++NH3=CuNH332+ k3=1.1103 CuNH332++NH3=CuNH342+ k4 =2.01022.chelate EDTA-EDTAethylenediamine tetraacetic acid

  • EDTA1.EDTA -EDTA-H4Y0.02g/100mL EDTA-EDTA-Na2H2Y2H2O11.1g/100mL0.3mol/L, pH4.40.010.02mol/L

  • 2EDTA 76

    _1056919701.unknown

    _1056919820.unknown

    _1056919907.unknown

    _1056919947.unknown

    _1056919978.unknown

    _1056919876.unknown

    _1056919771.unknown

    _1056919772.unknown

    _1056919723.unknown

    _1056919609.unknown

    _1056919675.unknown

    _1056919565.unknown

  • * pH 1H6Y* pH 2.67~6.16H2Y* pH 10.26Y

  • 311H+

    M++H2Y2-=MY3-+2H+M2++H2Y2-=MY2-+2H+M3++H2Y2-=MY-+2H+M4++H2Y2-=MY+2H+

  • (4) EDTA

    4-1 EDTA

    CoY

    Fe(OH)Y2-

    pH=6

    CrY-

    FeY-

    Cr(OH)Y2-

    pH>10

    MnY2-

    CuY2-

    NiY2-

  • 4.2 1 2 3

  • (stability constant)-formation constant* n=11 M + Y = MY

    * instability constant K=1/K

  • *stepwise stability constantMLn1n

    _1056921157.unknown

    _1056921237.unknown

    _1056921309.unknown

    _1056921329.unknown

    _1056921211.unknown

    _1056921140.unknown

  • *cumulative stability constant

    n

    _1056921459.unknown

    _1057215365.unknown

    _1056921413.unknown

  • 1 McMLCl[L]cM

    _1057151334.unknown

    _1057151422.unknown

    _1057151293.unknown

  • lg[Cl-]-5~-3Hg2+Cl-HgCl2

  • (2) CMCL[L]

    [Cl-]=10-3.20mol/L[Cl-]=10-4.20mol/Ln=2

  • 4.3 1 2 Y M MY3 4

  • 4.3 side reaction MYMYM,YMY

  • side reaction coefficient1.Y1EDTAYHacidic effect acidic effective coefficient MEDTA[Y]Y[Y]YYH

    *YEDTA Y=1

  • acidic effective curve

  • 2 NYYN

    [Y]NYYKNYNY[N]N

  • 3YY NY

  • 2.M1 MLML[M]

    *MLMML=1

  • 2MM

    8 pH=10.0, OH-

    9 pH=12.0, NH3

  • 3 MYMHYM(OH)Y

  • (conditional stability constant) apparent stability constant

    10 AlY

  • *

    * MLpM*MLnL

  • 4.4 ( matallochromic indicator )1 2 3 4

  • 4.4 M + In = MIn MIn + Y = MY + In * (1) MInIn (2) (3) MIn (4)

  • pMpMeppMsp

    [MIn]=[In]

  • 1.(blocking of indicator) In EBTEDTACa2+Mg2+Al3+Fe3+

  • 2. ossification of indicator MInMIn PAN

  • In MIn pH TEBT 711 XO 56 1-2- 212-2-PAN 1013EBT - eriochrome black TXO - xylenol organgePAN - 1-(2-pyridylazo)-2-naphthol calconcarboxylic acid

  • 4.5 1 2 3 4

  • 4.5 1.titration index

  • 2.1KMYKMY
  • 12 13 14*

    *Ringbom

  • 12 pH=10.00T0.020 molL-1EDTA0.020 molL-1Ca2+0.020 molL-1Mg2+ Ca2+ Et=-1.5% Mg2+ Et=0.11% TCaYMgYTCa2+

  • *Et0.1%pM=0.2 lgCMspKMY6 lgCMspKMY6. CM=0.010 mol/LlgKMY8

    *Et1% lgCMspKMY4

  • NM: Et0.3%pM=0.2 lgCMspKMY=lgCMspKMY-lgCNspKNY =lgKC5

  • 4.6 1. CM=0.010 mol/LEt0.1%pM=0.2

    =logKMY -8 10pH

  • 2. 16 0.020 molL-1EDTA0.020 molL-1Fe3+ =0.2 =17.1 pH1.2 pH=2.1Fe3+pH=1.2-2.1

  • M10-2 molL-1EDTABi3+Pb2+Bi3+ pH= 1.4

  • 4.7 MN ,.1, N.2NKNYNYM3X

  • *M M logCM KMY6 NM logcK= logCM KMY- logCN KNY6 Bi3+Pb2+logcK=9.9, pH=1.0XOBi3+ pH=5.5XOBi3+

  • masking.MNNLN*EDTAM Al3+Zn2+Al3+F-pH5~6Al3+AlF63-EDTAZn2+Al3+

  • *LNNL EDTA MXNLNL NEDTANX KCNCu2+Zn2+TEDTAPb2+Pb2+(), ZnCN42-Zn2+EDTAZn2+

  • *EDTAM,NL,LNYN, YYN Al3+Ti(IV)EDTAAlYTiYNH4F(NaF)EDTAAlTiTiYEDTATiAl, TiTiAl

  • .KCN,, Cu2+,Co2+,Ni2+,Hg2+Zn2+,Cd2+ Ca2+,Mg2+,Pb2+

  • NH4FNaF Al3+Ti(IV)Zr(IV)Sn(IV)Th(IV) EDTANH4FEDTAEDTAEDTA

  • pH=5~6Al3+Fe3+Be2+Pd2+UO2+2, YPb2+Zn2+Mn2+Co2+Ni2+Cd2+Bi3+Sn2+ Bi3+Cr3+Fe3+Sn(IV)Th(IV)Ti(IVYCu2+Hg2+Cd2+Pb2+Zn2+ Fe3+Al3+YMn2+ Fe3+Al3+Mn2+

  • Al3+Th(IV)Zr(IV)1,10- pH=5~6Cu2+Ni2+Zn2+Cd2+Hg2+Co2+Mn2+ Fe2+Cu2+Ni2+Co2+Zn2+Cd2+Hg2+ Fe3+Al3+Ti(IV)Sn(IV)Mn2+

  • EDTACa2+Mg2+Mg(OH)2Ca2+OH-Mg2+

  • Fe3+ Fe2+ Na2S2O3 Cu2+ CuS2O323- Cr3+ Cr2O72-

  • 3.8

  • 40 Ca2+Mg2+Bi3+Fe3+Pb2+Cu2+Zn2+Cd2+Mn2+Fe2+

  • Al3+Cr3+Co2+Ni2+TiSn

    Al3+ Al3+Y pH3.5pH5~6 Zn2+Y

  • . 2Ag+ + NiCN42 2AgCN2+ Ni2+

    .EDTA MY + L = ML + Y SnY + 6F- = SnF62- + Y

  • Al3+TiPb2+Zn2+Al3+Ti

    Al3+ AlY Zn2+ Ti + YTiOY + Y ZnY Pb2+ PbY Zn2+ ZnY

    +NH4F AlTi + Ti

  • EDTANa+K+SO42PO43CN

  • p196 1p197 4 5 6 7 8 9 10 11 p198 12 14 17 19 20 22 p199 26 28 29 30 31 32 p200 35

  • p132 23567 p133 910 p134 17 p135 19