第 2 章 酸碱滴定法 Acid-base titration
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Transcript of 第 2 章 酸碱滴定法 Acid-base titration
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2 Acid-base titration2.1 2.2 2.3 pH2.4 2.5 2.6 2.7 2.8
Anal. Chem. ZSU.
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2.1 1 2 3 4 Anal. Chem. ZSU.
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2.1 1 1cKac apH 2pHKapH014EDTAH6Y2+Y4-ipH 3c 4 5
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2.1 2 pHAnal. Chem. ZSU.
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2.1 3 concentration, activity , activity coefficient = iC ii1=c
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2.1 1 23Anal. Chem. ZSU.
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2.1 (ionic strength)
AB
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2.1 4 11HAcAc- H2OHCO32-(amphoteric substance)Anal. Chem. ZSU.
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2.1 (conjugate acid-base pair) Ka Kb = Kw =1.0 10-14Anal. Chem. ZSU.
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2.1 Anal. Chem. ZSU.
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2.2 1 (analytical concentration)C
equilibrium concentration [ ]Anal. Chem. ZSU.
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2.2 2 aciditymolH+pHbasicitymolOH-pOH
Anal. Chem. ZSU.
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2.2 3 distribution coefficient) H+ 1Anal. Chem. ZSU.
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2.2 4 distribution diagram1monacid solutionHAcHAcAc-Anal. Chem. ZSU.
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2.2 * Ac-pH HAcpH* pH=pKa4.74 Ac- = HAc =0.50, HAcAc-* pHpKa Ac-*cpHpKa [HAc][Ac-] cAnal. Chem. ZSU.
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2.2 2dibasic acid solutionH2C2O4 HC2O4- C2O42 0Anal. Chem. ZSU.
- 2.2 pH* pH
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2.2 3polyprotic acid solution H3PO4H2PO4-1HPO42-PO43-Anal. Chem. ZSU.
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2.2 Anal. Chem. ZSU.
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2.3 pH1 2 pH* * * * * Anal. Chem. ZSU.
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2.3 pH1 (material balance equation) MBE c (mol/L) HAc
c (molL-1)Na2SO3
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2.3 pHCharge balance equationCBEmolmol cmolL-1NaCN:[H+] + [Na+] = [CN-] + [OH-] [H+] + c = [CN-] + [OH-] cmolL-1CaCl2:[H+] + 2[Ca2+]=[OH-]+[Cl-]Anal. Chem. ZSU.
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2.3 pHProton balance equationPBE HAc
Na2S[OH-]
NaHCO3Anal. Chem. ZSU.
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2.3 pHAnal. Chem. ZSU.
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2.3 pHNH4H2PO4+H+ -H+H+ H2O OH- NH4+ NH3H3PO4H2PO4-HPO42- H2PO4- PO43- [H+]+[H3PO4]=[OH-]+[NH3]+2[PO43-]+[HPO42-]Anal. Chem. ZSU.
- 2.3 pH2 pH1 A [H+]=Ca Ca10-6mol/L B Ca
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2.3 pH A [OH-]=Cb Cb10-6mol/LB
Cb
- 2.3 pH2678A CKa20KwC/Ka500B CKa20KwC/Ka
- 2.3 pH 9A CKb20KwC/Kb500B CKb20KwC/Kb
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2.3 pH 1112ACKa120Kw C/Ka1500
B CKa120Kw
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2.3 pH3 Ca mol/L HCl + C mol/L HAcA [H+]Ca Ca20[Ac-]B
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2.3 pH413 HA CHA KHA HB CHB KHB
CHAKHA>>CHB KHB
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2.3 pH5
CB1KHB1>>CB2 KHB2Anal. Chem. ZSU.
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2.3 pH6 NaHA 141516 [HA-]CHA-
[HA-]CKa2>20KwHA-
[HA-]CKa2>20Kw C> 20Ka1Anal. Chem. ZSU.
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2.3 pH NH4AcNH4F 1718 [HA]=[A-]CHAA-
[HA]=[A-]CKa20KwHAA-
[HA]=[A-]CKa20Kw C> 20KaAnal. Chem. ZSU.
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2.3 pH NH42CO3NH42S
19 Anal. Chem. ZSU.
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2.3 pH HAc + NaFH3BO3 + NaAc20
KHAcCHAc20KwCF-20KHF
Anal. Chem. ZSU.
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2 p82 3 p84 3710p83 10 bf p85 151620p83 12 c p86 21p83 1 bcd 2 cdh
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2 Acid-base titration2.4 2.5 2.6 2.7 2.8 Anal. Chem. ZSU.
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2.4 1 2 pH3 4 5 Anal. Chem. ZSU.
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2.4 1 Buffer solutionpH212HAc-Ac-NH4Cl-NH3pH12Anal. Chem. ZSU.
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2.4 2 pH212223 pH6
pH8CaCb20[H+]CaCb20[OH-] Anal. Chem. ZSU.
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2.4 Anal. Chem. ZSU.
21 0.10 molL-1
0.20molL-1
pH.
2-33
=9.56
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2.4 3 buffer index
pH pH pHpH=pKa1 Ca/Cb=11pKa=pHAnal. Chem. ZSU.
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2.4 4 buffer capacityCpHpHpH =C=pH=2A--1A-CHA 2A-1A-pH2pH1CHACa/Cb0011mol/LCa/Cb1/1010/111Anal. Chem. ZSU.
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2.4 Anal. Chem. ZSU.
pH=pKa1
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2.4 5 5 pHpKapHpKapH Anal. Chem. ZSU.
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2.5 1 2 3 4
Anal. Chem. ZSU.
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2.5 1 indicatorpHAnal. Chem. ZSU.
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2.5 methyl orangeMO)-
pH 3.1, pH 4.4, pH 3.1-4.4Anal. Chem. ZSU.
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2.5 phenolphthalein PP-
methyl red MR- Anal. Chem. ZSU.
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2.5 2 HIn = H+ + In- 10 0.1 =1pH=pKa pH=PKa1
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2.5
pKHIn MO 3.1~4.4 3.4 MR 2.4~6.2 5.0 PP 8.0~9.6 9.1Anal. Chem. ZSU.
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2.5 3 pH 18 100 MO 3.1~4.4 2.5~3.7 PP 8.0~9.6 8.1~9.0pH
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2.5 4 mixed indicator pH 0.3pH0.2pHAnal. Chem. ZSU.
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2.5 Anal. Chem. ZSU.
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2.6 1 2 3 4 5 Anal. Chem. ZSU.
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2.6 1 titration curvepHfraction titratedtitration jump0.999 1.001pH pKa0.1%0.1 mol/LAnal. Chem. ZSU.
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2.6 2 NaOHHCl
NaOH0.1000 mol/LVb0mL~40mLHClNaOHVHCl20.00mLa
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2.6
pHsp=7.00pH4.30-9.70pKaAnal. Chem. ZSU.
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2.6 10pHpH1mol/L 3.3~10.730.1 mol/L4.30~9.7020.01 mol/L 5.3~8.7CO2Anal. Chem. ZSU.
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2.6 HClNaOH
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2.6 3 0.1 mol/LNaOHHAcpHsp8.72pH7.74~9.70Anal. Chem. ZSU.
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2.6 Ka
KaAnal. Chem. ZSU.
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2.6
0.1 mol/LHClNH3pHsp5.28pH4.30~6.25Anal. Chem. ZSU.
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2.6 4 NaOH0.10 mol/L H3PO4 pHsp1=4.70 pHsp2=9.66
* CKa110-8 * Ka 105 Anal. Chem. ZSU.
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2.6 :
HAKa c1 HBKa c2
HBHA
H2SO4+NH4Cl
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2.6
HClNa2CO3pHsp1 =8.3 pHsp2 =3.9 Anal. Chem. ZSU.
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2.6 5 C 10-4 mol/L Cka 10-8 Ckb 10-8NaHA Cka2 10-8NaHA Ckb2 10-8 Ka 105 Kb 105 C1Ka1/C2ka2 105Anal. Chem. ZSU.
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2.6
CO2Anal. Chem. ZSU.
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2.7 (end point error,titration errror) 1 2 3 Anal. Chem. ZSU.
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2.7 1 Anal. Chem. ZSU.
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2.7 2 Anal. Chem. ZSU.
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2.7 3 H3A
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2.8 1 a b 2 3 a b Anal. Chem. ZSU.
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2.8 1 NaOH+Na2CO3* BaCl2 +HCl ---- +BaCl2 +HCl ---NaOH* NaOH --- Na2CO3 Anal. Chem. ZSU.
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2 p82 3 p84 3710p83 10 bf p85 151620p83 12 c p86 21p83 1 bcd 2 cdhAnal. Chem. ZSU.