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H 2 CO 3 ( a q ) + H 2 O ( l ) H 3 O + ( a q ) + HCO 3 ( a q ) K a 1 = 4.3 × 10 −7
HCO 3 ( a q ) + H 2 O ( l ) H 3 O + ( a q ) + CO 3 2− ( a q ) K a2 = 5.6 × 10 −11

Solution

As indicated by the ionization constants, H 2 CO 3 is a much stronger acid than HCO 3 , so H 2 CO 3 is the dominant producer of hydronium ion in solution. Thus there are two parts in the solution of this problem: (1) Using the customary four steps, we determine the concentration of H 3 O + and HCO 3 produced by ionization of H 2 CO 3 . (2) Then we determine the concentration of CO 3 2− in a solution with the concentration of H 3 O + and HCO 3 determined in (1). To summarize:

Four tan rectangles are shown that are connected with right pointing arrows. The first is labeled “left bracket H subscript 2 C O subscript 3 right bracket.” The second is labeled “left bracket H subscript 3 O superscript plus right bracket and left bracket H C O subscript 3 superscript negative right bracket from H subscript 2 C O subscript 3.” The third is labeled “left bracket C O subscript 3 superscript 2 negative right bracket from H C O subscript 3 superscript negative.”
  1. Determine the concentrations of H 3 O + and H C O 3 .
    H 2 CO 3 ( a q ) + H 2 O ( l ) H 3 O + ( a q ) + HCO 3 ( a q ) K a 1 = 4.3 × 10 −7

    As for the ionization of any other weak acid:
    Four tan rectangles are shown that are connected with right pointing arrows. The first is labeled “Determine the direction of change.” The second is labeled “Determine x and the equilibrium concentrations.” The third is labeled “Solve for x and the equilibrium concentrations.” The fourth is labeled “Check the math.”
    An abbreviated table of changes and concentrations shows:
    This table has two main columns and four rows. The first row for the first column does not have a heading and then has the following in the first column: Initial concentration ( M ), Change ( M ), Equilibrium constant ( M ). The second column has the header of “H subscript 2 C O subscript 3 plus sign H subscript 2 O equilibrium arrow H subscript 3 O superscript positive sign plus sign H C O subscript 3 superscript negative sign.” Under the second column is a subgroup of three columns and three rows. The first column has the following: 0.033, negative sign x, 0.033 minus sign x. The second column has the following: approximately 0, x, x. The third column has the following: 0, x, x.
    Substituting the equilibrium concentrations into the equilibrium gives us:
    K H 2 CO 3 = [ H 3 O + ] [ HCO 3 ] [ H 2 CO 3 ] = ( x ) ( x ) 0.033 x = 4.3 × 10 −7

    Solving the preceding equation making our standard assumptions gives:
    x = 1.2 × 10 −4

    Thus:
    [ H 2 CO 3 ] = 0.033 M

    [ H 3 O + ] = [ HCO 3 ] = 1.2 × 10 −4 M
  2. Determine the concentration of C O 3 2− in a solution at equilibrium with [ H 3 O + ] and [ H C O 3 ] both equal to 1.2 × 10 −4 M .
    HCO 3 ( a q ) + H 2 O ( l ) H 3 O + ( a q ) + CO 3 2− ( a q )

    K HCO 3 = [ H 3 O + ] [ CO 3 2− ] [ HCO 3 ] = ( 1.2 × 10 −4 ) [ CO 3 2− ] 1.2 × 10 −4

    [ CO 3 2− ] = ( 5.6 × 10 −11 ) ( 1.2 × 10 −4 ) 1.2 × 10 −4 = 5.6 × 10 −11 M

To summarize: In part 1 of this example, we found that the H 2 CO 3 in a 0.033- M solution ionizes slightly and at equilibrium [H 2 CO 3 ] = 0.033 M ; [ H 3 O + ] = 1.2 × 10 −4 ; and [ HCO 3 ] = 1.2 × 10 −4 M . In part 2, we determined that [ CO 3 2− ] = 5.6 × 10 −11 M .

Check your learning

The concentration of H 2 S in a saturated aqueous solution at room temperature is approximately 0.1 M . Calculate [ H 3 O + ] , [HS ], and [S 2− ] in the solution:

H 2 S ( a q ) + H 2 O ( l ) H 3 O + ( a q ) + HS ( a q ) K a 1 = 8.9 × 10 −8
HS ( a q ) + H 2 O ( l ) H 3 O + ( a q ) + S 2− ( a q ) K a 2 = 1.0 × 10 −19

Answer:

[H 2 S] = 0.1 M ; [ H 3 O + ] = [HS ] = 0.000094 M ; [S 2− ] = 1 × 10 −19 M
We note that the concentration of the sulfide ion is the same as K a2 . This is due to the fact that each subsequent dissociation occurs to a lesser degree (as acid gets weaker).

A triprotic acid    is an acid that has three dissociable protons that undergo stepwise ionization: Phosphoric acid is a typical example:

First ionization: H 3 PO 4 ( a q ) + H 2 O ( l ) H 3 O + ( a q ) + H 2 PO 4 ( a q ) K a 1 = 7.5 × 10 −3 Second ionization: H 2 PO 4 ( a q ) + H 2 O ( l ) H 3 O + ( a q ) + HPO 4 2− ( a q ) K a 2 = 6.2 × 10 −8 Third ionization: HPO 4 2− ( a q ) + H 2 O ( l ) H 3 O + ( a q ) + PO 4 3− ( a q ) K a 3 = 4.2 × 10 −13

As with the diprotic acids, the differences in the ionization constants of these reactions tell us that in each successive step the degree of ionization is significantly weaker. This is a general characteristic of polyprotic acids and successive ionization constants often differ by a factor of about 10 5 to 10 6 .

This set of three dissociation reactions may appear to make calculations of equilibrium concentrations in a solution of H 3 PO 4 complicated. However, because the successive ionization constants differ by a factor of 10 5 to 10 6 , the calculations can be broken down into a series of parts similar to those for diprotic acids.

Polyprotic bases can accept more than one hydrogen ion in solution. The carbonate ion is an example of a diprotic base    , since it can accept up to two protons. Solutions of alkali metal carbonates are quite alkaline, due to the reactions:

Practice Key Terms 5

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Source:  OpenStax, Ut austin - principles of chemistry. OpenStax CNX. Mar 31, 2016 Download for free at http://legacy.cnx.org/content/col11830/1.13
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