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14.6 Buffers  (Page 11/9)

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By the end of this section, you will be able to:
  • Describe the composition and function of acid–base buffers
  • Calculate the pH of a buffer before and after the addition of added acid or base

A mixture of a weak acid and its conjugate base (or a mixture of a weak base and its conjugate acid) is called a buffer solution, or a buffer    . Buffer solutions resist a change in pH when small amounts of a strong acid or a strong base are added ( [link] ). A solution of acetic acid and sodium acetate (CH 3 COOH + CH 3 COONa) is an example of a buffer that consists of a weak acid and its salt. An example of a buffer that consists of a weak base and its salt is a solution of ammonia and ammonium chloride (NH 3 ( aq ) + NH 4 Cl( aq )).

Two images are shown. Image a on the left shows two beakers that each contain yellow solutions. The beaker on the left is labeled “Unbuffered” and the beaker on the right is labeled “p H equals 8.0 buffer.” Image b similarly shows 2 beakers. The beaker on the left contains a bright orange solution and is labeled “Unbuffered.” The beaker on the right is labeled “p H equals 8.0 buffer.”
(a) The buffered solution on the left and the unbuffered solution on the right have the same pH (pH 8); they are basic, showing the yellow color of the indicator methyl orange at this pH. (b) After the addition of 1 mL of a 0.01- M HCl solution, the buffered solution has not detectably changed its pH but the unbuffered solution has become acidic, as indicated by the change in color of the methyl orange, which turns red at a pH of about 4. (credit: modification of work by Mark Ott)

How buffers work

A mixture of acetic acid and sodium acetate is acidic because the K a of acetic acid is greater than the K b of its conjugate base acetate. It is a buffer because it contains both the weak acid and its salt. Hence, it acts to keep the hydronium ion concentration (and the pH) almost constant by the addition of either a small amount of a strong acid or a strong base. If we add a base such as sodium hydroxide, the hydroxide ions react with the few hydronium ions present. Then more of the acetic acid reacts with water, restoring the hydronium ion concentration almost to its original value:

CH 3 CO 2 H ( a q ) + H 2 O ( l ) ⟶ H 3 O + ( a q ) + CH 3 CO 2 − ( a q )

The pH changes very little. If we add an acid such as hydrochloric acid, most of the hydronium ions from the hydrochloric acid combine with acetate ions, forming acetic acid molecules:

H 3 O + ( a q ) + CH 3 CO 2 − ( a q ) ⟶ CH 3 CO 2 H ( a q ) + H 2 O ( l )

Thus, there is very little increase in the concentration of the hydronium ion, and the pH remains practically unchanged ( [link] ).

This figure begins with a chemical reaction at the top: C H subscript 3 C O O H ( a q ) plus H subscript 2 O ( l ) equilibrium arrow H subscript 3 O superscript positive sign ( a q ) plus C H subscript 3 C O O superscript negative sign ( a q ). Below this equation are two arrows: one pointing left and other pointing right. The arrow pointing left has this phrase written above it, “H subscript 3 O superscript positive sign added, equilibrium position shifts to the left.” Below the arrow is the reaction: C H subscript 3 C O O H ( a q ) left-facing arrow C H subscript 3 C O O superscript negative sign ( a q ) plus H subscript 3 O superscript positive sign. The arrow pointing right has this phrase written above it, “O H subscript negative sign added, equilibrium position shifts to the right.” Below the arrow is the reaction: O H superscript negative sign plus C H subscript 3 C O O H ( a q ) right-facing arrow H subscript 2 O ( l ) plus C H subscript 3 C O O superscript negative sign ( a q ). Below all the text is a figure that resembles a bar graph. In the middle are two bars of equal height. One is labeled, “C H subscript 3 C O O H,” and the other is labeled, “C H subscript 3 C O O superscript negative sign.” There is a dotted line at the same height of the bars which extends to the left and right. Above these two bars is the phrase, “Buffer solution equimolar in acid and base.” There is an arrow pointing to the right which is labeled, “Add O H superscript negative sign.” The arrow points to two bars again, but this time the C H subscript 3 C O O H bar is shorter than that C H subscript 3 C O O superscript negative sign bar. Above these two bars is the phrase, “Buffer solution after addition of strong base.” From the middle bars again, there is an arrow that points left. The arrow is labeled, “Add H subscript 3 O superscript positive sign.” This arrow points to two bars again, but this time the C H subscript 3 C O O H bar is taller than the C H subscript 3 C O O superscript negative sign bar. These two bars are labeled, “Buffer solution after addition of strong acid.”
This diagram shows the buffer action of these reactions.

A mixture of ammonia and ammonium chloride is basic because the K b for ammonia is greater than the K a for the ammonium ion. It is a buffer because it also contains the salt of the weak base. If we add a base (hydroxide ions), ammonium ions in the buffer react with the hydroxide ions to form ammonia and water and reduce the hydroxide ion concentration almost to its original value:

NH 4 + ( a q ) + OH − ( a q ) ⟶ NH 3 ( a q ) + H 2 O ( l )

If we add an acid (hydronium ions), ammonia molecules in the buffer mixture react with the hydronium ions to form ammonium ions and reduce the hydronium ion concentration almost to its original value:

H 3 O + ( a q ) + NH 3 ( a q ) ⟶ NH 4 + ( a q ) + H 2 O ( l )

The three parts of the following example illustrate the change in pH that accompanies the addition of base to a buffered solution of a weak acid and to an unbuffered solution of a strong acid.

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Source:  OpenStax, Chemistry. OpenStax CNX. May 20, 2015 Download for free at http://legacy.cnx.org/content/col11760/1.9
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