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    Polyprotic Acids and Bases

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    Polyprotic Acids and Bases

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    Polyprotic Acids And Bases

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    00:52, 13 Feb 2017
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    Table of contents

    The name "polyprotic" literally means many protons. Therefore, in this section we will be
    observing some specific acids and bases which either lose or accept more than one proton.
    Then, we will be talking about the equations used in finding the degree of dissociation.
    Finally, with given examples, we will be able to approach problems dealing with polyprotic
    acids and bases.

    Introduction
    Polyprotic acids are specific acids that are capable of losing more than a single proton per
    molecule in acid-base reactions. (In other words, acids that have more than one ionizable
    H+atom per molecule). Protons are lost through several stages (one at each stage), with the
    first proton being the fastest and most easily lost. Contrast with monoprotic acids in
    section Monoprotic Versus Polyprotic Acids And Bases.

    Commo Formu Strong/ Number Ka1 Ka2 Ka3


    n la Weak of
    Polyprot Acid Ionizabl
    ic Acids e
    Hydroge
    ns

    Sulfuric H2SO4 Strong 2 Ver 1.1


    acid (diprotic) y E-2
    Lar
    ge

    Sulfurous H2SO3 Weak 2 1.3 6.2


    acid (diprotic) E-2 E-8

    Phosphori H3PO4 Weak 3 7.1 6.3 4.2


    Commo Formu Strong/ Number Ka1 Ka2 Ka3
    n la Weak of
    Polyprot Acid Ionizabl
    ic Acids e
    Hydroge
    ns

    c acid (triprotic) E-3 E-8 E-


    13

    Carbonic H2CO3 Weak 2 4.4 4.7


    acid (diprotic) E-7 E-
    11

    Hydrosulf H 2S Weak 2 1.0 1E-


    uric acid (diprotic) E-7 19
    or
    Hydrogen
    sulfide

    Oxalic H 2C 2O 4 Weak 2 5.4 5.3


    acid (diprotic) E-2 E-5

    Malonic H 2C 3H 2 Medium 2 1.5 2.0


    acid O4 Strong (diprotic) E-3 E-6

    From the table above, we see that sulfuric acid is the strongest.

    Ionization Constant
    It is important to know that K 1>K2>K3, where K stands for the acidity constant or acid
    ionization constant (first, second, and third, respectively). These constants are used to
    measure the degree of dissociation of hydrogens in the acid. For a more in depth discussion
    on this, go to Ionization Constants.

    Example 1: Hydrosulfuric acid


    To find Ka1 of Hydrosulfuric acid (H2S), you must first write the reaction:
    H2S⇌H++HS−H2S⇌H++HS−

    Dividing the products by the reactants, we then have:

    Ka1=[H+][HS−][HS−]Ka1=[H+][HS−][HS−]

    To find Ka2, we start with the reaction:

    HS−⇌H++S−2HS−⇌H++S2−

    Then, like when finding Ka1Ka1, write the products over the reactants:

    Ka2=[H+][S−2][HS−]Ka2=[H+][S2−][HS−]

    From these reactions we can observe that it takes two steps to fully remove the H + ion. This
    also means that this reaction will produce two equivalence points or stoichiometric points.
    The equivalence point, by definition, is the point during an acid-base titration in which there
    has been equal amounts of acid and base reacted. If we were to graph this, we would be able
    to see exactly just what two equivalence points looks like. Let's check it out:

    Note the multiple equivalence points and notice that they are almost straight lines at that
    point, indicating equal added quantities of acid and base.

    Titrations
    In strong acid + strong base titrations, the pH changes slowly at first, rapidly through the
    equivalence point of pH=7, and then slows down again. If it is being titrated in a strong acid,
    the pH will go up as the base is added to it. Conversely, if it is in a strong base, the pH will
    fall down as acid is added.

     In strong acid + weak base titrations, the pH changes slowly at the equivalence point and
    the pH equals the pKa of the acid. The pH is below 7.
     For the weak acid + strong base, the pH is above 7 at the equivalence point.
     If there is strong acid or strong base left over after the equivalence point, this can be used
    to find the pH of the solution.

    Next, let's take a look at sulfuric acid. This unique polyprotic acid is the only one to be
    completely deprotonated after the first step:

    H2SO4(aq)+H2O(l)⇌H3O+(aq)+HSO−4(aq)H2SO4(aq)+H2O(l)⇌H3O(aq)++HSO4(aq)−
    Now let's try something a little harder. The ionization of phosphoric acid (three dissociation
    reactions this time) can be written like this:

    Start with H3PO4:

    Ka1:H3PO4(aq)⇌H+(aq)+H2PO−4(aq)Ka1:H3PO4(aq)⇌H(aq)++H2PO4(aq)−
    Ka2:H2PO−4(aq)⇌HPO4(aq)+H+(aq)Ka2:H2PO4(aq)−⇌HPO4(aq)+H(aq)+
    Ka3:HPO−4(aq)⇌H+(aq)+PO3−4(aq)Ka3:HPO4(aq)−⇌H(aq)++PO4(aq)3−

    So from these above reactions we can see that it takes three steps to fully remove the H + ion.
    This also means that this reaction will produce three equivalence points. Polyprotic
    Bases are bases that can accept at least one H+ ion, or proton, in acid-base reactions.

    olyprotic Bases Formula Strong/Weak Base

    sphate ion PO43- Weak

    ulfate ion SO42- Very Weak

    bonate ion CO32- Strong

    Example 2: Some examples for calculating the constant, Kb


    First, start with the reaction A3- + H2O ? HA2- + OH-

    Kb1= [OH-][HA2-]/[A3-]=KW/Ka3

    Then, we plug in the products over the reactants:

    HA2- + H2O ? H2A- + OH-

    Kb2 = [OH-][H2A2-]/[HA2-]=KW/Ka2

    Finally, we are left with the third dissociation, or Kb3:

    H2A- + H2O ? H3A + OH-

    Kb3 = [OH-][H3A]/[H2A-]=KW/Ka1
    References
    1. Petrucci, et al. General Chemistry: Principles & Modern Applications: AIE (Hardcover).
    Upper Saddle River: Pearson/Prentice Hall, 2007.

    Contributors
     Natalie Kania
    1. Back to top
    2.
    o Polyprotic Acids & Bases

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