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    H3PO4

    Uploaded by

    Je Rivas
    This document discusses titrations of polyprotic acids. It defines polyprotic acids as acids that can donate more than one proton. It gives the example of phosphoric acid H3PO4 and its acid dissociation constants Ka1, Ka2, and Ka3. It explains that the Ka values are multiplied when consecutive equilibria are considered. It also discusses how the titration curve of a diprotic acid like H2A has multiple endpoints observable when the Ka values differ by more than 3 orders of magnitude. It provides details on interpreting the pH at various points in the titration process. Finally, it compares linear segment and sigmoidal titration curves and discusses methods for determining equivalence points.

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    © All Rights Reserved
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    H3PO4

    Uploaded by

    Je Rivas
    284 views12 pages
    This document discusses titrations of polyprotic acids. It defines polyprotic acids as acids that can donate more than one proton. It gives the example of phosphoric acid H3PO4 and its acid dissociation constants Ka1, Ka2, and Ka3. It explains that the Ka values are multiplied when consecutive equilibria are considered. It also discusses how the titration curve of a diprotic acid like H2A has multiple endpoints observable when the Ka values differ by more than 3 orders of magnitude. It provides details on interpreting the pH at various points in the titration process. Finally, it compares linear segment and sigmoidal titration curves and discusses methods for determining equivalence points.

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    titration

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    This document discusses titrations of polyprotic acids. It defines polyprotic acids as acids that can donate more than one proton. It gives the example of phosphoric acid H3PO4 and its acid dissociation constants Ka1, Ka2, and Ka3. It explains that the Ka values are multiplied when consecutive equilibria are considered. It also discusses how the titration curve of a diprotic acid like H2A has multiple endpoints observable when the Ka values differ by more than 3 orders of magnitude. It provides details on interpreting the pH at various points in the titration process. Finally, it compares linear segment and sigmoidal titration curves and discusses methods for determining equivalence points.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    284 views12 pages

    H3PO4

    Uploaded by

    Je Rivas
    This document discusses titrations of polyprotic acids. It defines polyprotic acids as acids that can donate more than one proton. It gives the example of phosphoric acid H3PO4 and its acid dissociation constants Ka1, Ka2, and Ka3. It explains that the Ka values are multiplied when consecutive equilibria are considered. It also discusses how the titration curve of a diprotic acid like H2A has multiple endpoints observable when the Ka values differ by more than 3 orders of magnitude. It provides details on interpreting the pH at various points in the titration process. Finally, it compares linear segment and sigmoidal titration curves and discusses methods for determining equivalence points.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    of 12
    At a glance
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    The key takeaways are that polyprotic acids can have multiple endpoints in a titration depending on the relative Ka values, and the pH at various points in a titration can be determined from the Ka values and concentrations of the acid and its conjugate bases.

    A useful indicator has reactions where the reactants and products can be easily distinguished and provide useful information, and the reaction proceeds quickly and efficiently. The proton transfer reaction of an indicator between its acid and conjugate base forms meets these criteria.

    When titrating with a pH meter, the equivalence point is identified as the point of greatest slope change on the first derivative curve or the inflection point on the second derivative curve.

    Titrations of polyprotic acids:

    Polyprotic acids and Ka values:


    H3PO4 + H2O
    H3O+ + H2PO4H2PO4- + H2O
    H3O+ + HPO42H3O+ + PO43HPO42- + H2O
    __________________________________
    3H3O+ + PO43-

    H3PO4 + 3H2O

    K a1

    [ H 3 O + ] H 2 PO4
    =
    = 7.11x10 3
    [H 3 PO4 ]

    Ka2

    [ H 3O + ] HPO42
    8
    =
    =
    6
    .
    32
    x
    10
    H 2 PO4

    Ka1=7.11x10-3
    Ka2=6.32x10-8
    Ka3=4.5x10-13
    Ka1Ka2Ka3

    [ H 3O + ] PO43
    K a3 =
    = 4.5 x1013
    2
    HPO4

    When consecutive equilibria are added, the Ka values


    are multiplied:
    H3PO4 + 2H2O
    2H3O+ + HPO42[ H 3O + ]2 HPO42
    K a1 K a 2 =
    = 4.49 x10 10
    [H 3 PO4 ]

    H3PO4 + 3H2O
    K a1 K a 2 K a 3

    3H3O+ + PO43-

    [ H 3O + ]3 PO43
    =
    = 2.0 x10 22
    [H 3 PO4 ]

    Titrations of polyprotic acids:


    multiple endpoints observable when Ka,n/Ka,n+1>103

    Titration curve of a weak diprotic acid H2A:


    1. pH before titration
    2. pH before first equiv. point
    3. pH at first equiv. pt.
    4. pH between equiv. pts.
    5. pH at second equiv. pt.
    6. pH after second equiv. pt.

    H2A + H2O
    HA- + H2O

    H3O+ + HAH3O+ + A2-

    Ka1
    Ka2

    1. pH prior to titration:
    for a strong diprotic acid, same as strong acid
    for a weak diprotic acid,
    if Ka1 > 103 Ka2, second equilibrium makes little
    contribution
    assuming autoprotolysis contributes little
    +

    [ H ] K a1CH 2 A or

    2.

    K a1 + K a21 + 4 K a C H 2 A
    [H ] =
    2
    +

    pH prior to first equiv. pt., 1st buffer region


    1st buffer region, both H2A and HA- present
    if Ka1 > 103 Ka2, second equilibrium makes little
    contribution, pH calculated like a normal buffer
    solution
    half way to equivalence, CH2A = CHA-

    [H+] = Ka1

    3.

    pH at first equiv. pt.


    solution is like that of a salt of a diprotic acid
    (e.g., NaHA)

    [H ] =
    +

    [
    [

    ]
    ]

    K a 2 HA + K w
    1 + HA K a1

    If it can be assumed that [HA-] CNaHA

    [H ]
    +

    K a 2C NaHA + K w
    1 + C NaHA K a1

    [ ]

    +
    If CNaHAKa1 > 10-13 and CNaHA/Ka1 > 100, H K a1K a 2

    4.

    pH in 2nd buffer region


    2nd buffer region, both HA- and A2- present
    if Ka1 > 103 Ka2, first equilibrium makes little
    contribution, pH calculated like a normal buffer
    solution
    half way to equivalence, CHA- = CA2-

    [H+] = Ka2

    5.

    pH at the second equivalence point


    Like a salt of A2-, main equilibrium is
    A2- + H2O

    OH- + HA-

    ][

    Kw
    OH HA
    K b1 =
    =
    Ka2
    A 2

    [ ]

    [OH ] K b1C A2

    or a more sophisticated relationship, if necessary


    6.

    pH beyond 2nd equiv. pt.


    treated like the addition of strong base to water

    Two common types of titration curves are used to


    determine equivalence points for any kind of titration:
    sigmoidal curves and linear-segment curve:
    linear segment curve

    Depends upon difference in instrument response


    between reactants and products. Intersection of
    response lines before and after equivalence point
    determined location of equivalence point. Data
    typically collected far from equivalence point.

    E.g. titration leading to complex formation


    Analyte
    + Reagent

    Complex
    lo response
    hi response
    lo response

    Analyte
    +
    lo response

    Reagent

    lo response

    Complex
    hi response

    Sigmoidal curve

    Plot(s) of p-function of analyte (e.g., pH or pOH)


    versus reagent volume. Careful measurements made
    near the equivalence point.
    Acid-base titrations usually make use of this
    approach. Reagent solutions are almost always a
    standardized solution of a strong acid or strong base
    because they give sharper end points than do weak
    acids or bases.

    Identifying equivalence points:


    1.

    titration with indicators (sigmoidal curve)

    2.

    titration with linear-segment curve

    3.

    titration monitored with a pH meter

    4.

    Gran plot (see feature 14-5, text)

    Titration monitored with a pH meter:

    1st derivative shows point of greatest slope eq. pt.


    2nd derivative indicates inflection point eq. pt.

    A bit about indicators:


    Characteristics of analytically useful chemical
    reactions:
    1.
    2.
    3.

    Reactants and products are easily distinguished


    The reaction provides useful information
    The reaction proceeds at high rates/efficiencies

    most acids and their conjugate bases are


    transparent to visible radiation
    pH indicators are exceptions, proton transfer
    reactions involving indicators meet the criteria for an
    analytically useful reaction

    pH transition range for an indicator:


    [H3O+] + [In-]

    HIn + H2O

    [H O ][In ]
    =
    +

    Ka

    [HIn]

    [ H 3O]+ = K a

    [HIn]

    [In ]

    color changes at ratios


    and

    [HIn]/In-] = 0.1
    [HIn]/[In-] = 10.0

    cannot be discerned by eye


    Hence, useful range for a pH indicator is:

    pH = pKa1

    Note: concentration of indicator must be minimized


    to avoid introduction of systematic error

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