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    Ch312 Lecture10 Ch16 w08 1

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    Angelyn Sayon
    Redox titrations involve the reaction of an oxidizing titrant with a reducing analyte. Three key points: 1) Before the equivalence point, the potential is calculated using the Nernst equation and varies with concentration. 2) At the equivalence point, the potential is the average of the standard potentials of the half-reactions. 3) For equal numbers of electrons in the half-reactions, the equivalence point potential is (E°titrant + E°analyte)/2. For unequal numbers, it is (mE°titrant + nE°analyte)/(m+n).

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    Ch312 Lecture10 Ch16 w08 1

    Uploaded by

    Angelyn Sayon
    57 views19 pages
    Redox titrations involve the reaction of an oxidizing titrant with a reducing analyte. Three key points: 1) Before the equivalence point, the potential is calculated using the Nernst equation and varies with concentration. 2) At the equivalence point, the potential is the average of the standard potentials of the half-reactions. 3) For equal numbers of electrons in the half-reactions, the equivalence point potential is (E°titrant + E°analyte)/2. For unequal numbers, it is (mE°titrant + nE°analyte)/(m+n).

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    Ch312-Lecture10-Ch16-w08-1

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    Redox titrations involve the reaction of an oxidizing titrant with a reducing analyte. Three key points: 1) Before the equivalence point, the potential is calculated using the Nernst equation and varies with concentration. 2) At the equivalence point, the potential is the average of the standard potentials of the half-reactions. 3) For equal numbers of electrons in the half-reactions, the equivalence point potential is (E°titrant + E°analyte)/2. For unequal numbers, it is (mE°titrant + nE°analyte)/(m+n).

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    © All Rights Reserved
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    Download as ppt, pdf, or txt
    57 views19 pages

    Ch312 Lecture10 Ch16 w08 1

    Uploaded by

    Angelyn Sayon
    Redox titrations involve the reaction of an oxidizing titrant with a reducing analyte. Three key points: 1) Before the equivalence point, the potential is calculated using the Nernst equation and varies with concentration. 2) At the equivalence point, the potential is the average of the standard potentials of the half-reactions. 3) For equal numbers of electrons in the half-reactions, the equivalence point potential is (E°titrant + E°analyte)/2. For unequal numbers, it is (mE°titrant + nE°analyte)/(m+n).

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    You are on page 1of 19

    Ch 16: Redox Titrations

    Redox titrations are essential in measuring the chemical composition of


    a superconductor (YBa2Cu3O7 - 2/3 Cu2+ and 1/3 the unusual Cu3+)
    KMnO4 Titrations
    8H+ + MnO4- +5e- = Mn2+ + 4H2O Eo = +1.51V
    permanganate is one of the strongest oxidizing agents available
    Preliminary Sample Treatment
    (from "Quantitative Analysis", 6th ed., Day and Underwood, 1991, p. 297)

    The iron in iron ore is usually both Fe2+ and Fe3+, so


    a reducing agent such as tin(II) chloride is used to
    convert it entirely to Fe2+.

    Step 1: Sn2+ + 2Fe3+ → Sn4+ + 2Fe2+ where the Sn2+ is added in excess
    Step 2: The excess Sn2+ that didn't react will react with the KMnO4, so it
    is removed by treating with HgCl2:
    2HgCl2 + Sn2+ → Hg2Cl2(s) + Sn4+ + 2Cl-
    Step 3: To prevent the reaction of Cl- with KMnO4, the Zimmerman-
    Reinhardt reagent is added. This reagent contains Mn2+ to
    prevent the oxidation of Cl- and H3PO4 prevents the formation of
    Fe3+-chloride complexes as the titration proceeds.
    KMnO4 Standardization Using Na2C2O4

    It takes 38.29 mL of a permanganate solution to titrate 0.2587


    g of preimary standard NaC2O4 (M = 133.999). What is the
    molarity of the permanganate?
    5C2O42- + 2MnO4- + 16H+ → 2Mn2+ + 10CO2 + 8H2O
    Determination of %Fe in an Ore

    A 0.4857 g iron ore sample was dissolved in concentrated


    acid and reduced to Fe2+ using SnCl2. 41.21 mL of 0.01963 M
    MnO4- was required to titrate the sample. Calculate the %Fe
    in the ore.
    MnO4- + 8H+ + 5Fe2+ → Mn2+ + 5Fe3+ + 4H2O
    Formal Potentials

    Redox System Standard Formal Solution


    Potential Potential
    Ce4+ + e- = Ce3+ --- 1.23 1 M HCl
    1.44 1 M H2SO4
    1.61 1 M HNO3
    1.7 1 M HClO4
    Fe3+ + e- = Fe2+ +0.771 0.68 1 M H2SO4
    0.700 1 M HCl
    0.767 1 M HClO4
    Cr2O72- + 14H+ + 6e- = 2Cr3+ + 7H2O +1.33 1.00 1 M HCl
    1.05 2 M HCl
    1.08 3 M HCl
    1.08 0.5 M H2SO4
    1.15 4 M H2SO4
    1.03 1 M HClO4
    H3AsO4 + 2H+ + 2e- = H3AsO3 + H2O +0.559 0.557 1 M HCl
    0.557 1 M HClO4
    Cr3+ + e- = Cr2+ -0.42 -0.38 1 M HClO4
    Theory of Redox Titrations (Sec 16-1)

    Titration reaction example -


    Ce4+ + Fe2+ → Ce3+ + Fe3+
    titrant analyte

    After the titration, most of the ions in


    solution are Ce3+ and Fe3+, but there will
    be equilibrium amounts of Ce4+ and
    Fe2+. All 4 of these ions undergoe redox
    reactions with the electrodes used to
    follow the titration. These redox
    reactions are used to calculate the
    potential developed during the titration.
    Saturated Calomel Reference Electrode half-reaction:
    2Hg(l) + 2Cl-(aq) = Hg2Cl2(s) + 2e- Eo = 0.241 V
    Pt electrode half-reactions:
    Fe3+ + e- = Fe2+ Eo' = 0.767 V*
    Ce4+ + e- = Ce3+ Eo' = 1.70 V*
    The net cell reaction can be described in two equivalent ways:
    2Fe3+ + 2Hg(l) + 2Cl- = 2Fe2+ + Hg2Cl2(s)
    2Ce4+ + 2Hg(l) + 2Cl- = 2Ce3+ + Hg2Cl2(s)

    * formal potential in 1.0 M HClO4


    1. Before the Equivalence Point
    It's easier to use the Fe half-reaction because we know how much
    was originally present and how much remains for each aliquot of
    added titrant (otherwise, using Ce would require a complicated
    equilibrium to solve for).

    E = E+ - E-
     [Fe 2 ] 
     0.767V - 0.0592 log 3 
     0.241V
     [Fe ] 

    Nernst equation for E- = Sat'd


    Fe3+ + e- = Fe2+ (n=1) Calomel
    Eo = 0.767V Electrode
    [Fe 2 ] voltage (ESCE)
     0.526V - 0.0592 log
    [Fe3 ]
    We're only going to calculate the potential at the half-
    equivalence point where [Fe2+] = [Fe3+]:
    0
    [Fe 2 ]
    E1/2  0.526V - 0.0592 log
    [Fe 3 ]

    E1/2 = 0.526V or more generally for the half-equivalence point:

    E1/2 = E+ - E- where E+ = Eo (since the log term went to zero)


    and E- = ESCE

    E1/2 = Eo - ESCE
    2. At the Equivalence Point

    Ce3+ + Fe3+ = Ce4+ + Fe2+ (reverse of the titration reaction)


    titrant analyte
    from the reaction stoichiometry, at the eq. pt. -
    [Ce3+] = [Fe3+]
    [Ce4+] = [Fe2+]
    the two ½ reactions are at equilibrium with the Pt electrode -
    Fe3+ + e- = Fe2+
    Ce4+ + e- = Ce3+
    so the Nernst equations are -
    [Fe 2 ] [Ce 3
    ]
    E   E0Fe - 0.0592 log E   ECe - 0.0592 log
    o

    [Fe 3 ] [Ce 4 ]
    [Fe 2 ]
    E   E0Fe - 0.0592 log
    [Fe 3 ] adding the two equations
    3 together gives -
    [Ce ]
    E   E Ce - 0.0592 log
    o

    [Ce 4 ]
    2 3
    [Fe ] [Ce ]
    2E   EFe  ECe - 0.0592 log
    o o
    3
    - 0.0592 log
    [Fe ] [Ce 4 ]
    2 3
    [Fe ] [Ce ]
    2E   EFe
    o
     E oCe - 0.0592 log
    [Fe3 ] [Ce 4 ]

    and since [Ce3+] = [Fe3+] and [Ce4+] = [Fe2+]


    2 3
    [Fe ] [Fe ]
    2E   EFe  ECe - 0.0592 log
    o o

    [Fe3 ] [Fe 2 ]
    2 3
    [Fe ] [Fe ]
    2E   EFe  ECe - 0.0592 log
    o o

    [Fe3 ] [Fe 2 ]

    2E   EFe
    o
     E oCe

    EFe
    o
     EoCe 0.767  1.70 2.467
    E     1.23V
    2 2 2

    More generally, this is the cathode


    E titrant  E analyte
    0 0
    potential at the eq. pt. for any redox
    E 
    2 reaction where the number of electrons in
    each half reaction is equal.

    Ee.p. = E+ - E- = E+ - ESCE = 1.23 - 0.241 = 0.99V


    Equivalence Point Potentials
    Use these equations with Standard Reduction Potentials!

    1. Equal number of electrons

    E 0titrant  E 0analyte
    E 
    2

    2. Unequal number of electrons (m = #e's cathode ½ rxn,


    n = #e's anode ½ rxn)

    mE 0titrant  nE0analyte
    E 
    mn
    Examples
    1. Equal number of electrons

    Fe2+ + Ce4+ = Fe3+ + Ce3+ in 1 M HClO4


    titrant

    2. Unequal number of electrons

    Sn4+ + 2Cr2+ = Sn2+ + 2Cr3+ in 1 M HCl


    titrant
    KMnO4 is its own indicator, and electrodes can be used also, in which
    case the eq. pt. is obtained by calculating the 2nd derivative. Otherwise, an
    indicator is chosen that changes color at the eq. pt. potential.

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