Practice Exercises

17.30 Will an aqueous solution of ammonium cyanide, NH CN, be acidic, basic, or neutral? (Hint:
These anions and cations are conjugates of an acid and a base listed in
Tables 17.2 and 17.3.) 17.31 Will an aqueous solution of ammonium nitrite, NH4NO2, be
acidic, basic, or neutral?

17.7|Buffer Solutions
Many chemical and biological systems are quite sensitive to pH. For
example, if the pH of your blood were to change from what it should be,
within the range of 7.35 to 7.42, either to 7.00 or to 8.00, you would die.
Lakes and streams with a pH less than 5 often cannot support fish life.
Thus, a change in pH can produce unwanted effects, and systems that
are sensitive to pH must be protected from the H+ or OH that might be
formed or con sumed by some reaction. Buffers are mixtures of solutes
that accomplish this. Such a solu tion is said to be buffered or it is described
as a buffer solution.

Composition of a Buffer A buffer contains solutes that enable it to

resist large changes in pH when small amounts of either strong acid or strong
base are added to it. Ordinarily, the buffer consists of two solutes, one a
weak Brønsted acid and the other its conjugate base. If the acid is molecular,
then the conjugate base is supplied by a soluble salt of the acid. For
example, a common buffer system consists of acetic acid plus sodium
acetate, with the salt's acetate ion serving as the Brønsted base. In your
blood, carbonic acid (H2CO3, a weak diprotic acid) and the bicarbonate ion
(HCO3, its conjugate base) serve as one of the buffer systems used to
maintain a remarkably constant pH in the face of the body's production of
organic acids by metabolism. Another common buffer consists of the weakly
acidic cation, NH4+, sup plied by a salt like NH4Cl, and its conjugate base,
NH3.
One important point about buffers is the distinction between keeping a solution at a particular pH and
keeping it neutral—at a pH of 7. Although it is certainly possible to buffer a
solution at pH 7, buffers can be made that will work at any pH value throughout
the pH scale.

How a Buffer Works

 tools
How buffers work

Not all the added H+ is

neutralized, so the pH is lowered a little.
Soon we'll see how much it changes.

To work, a buffer must be able to neutralize either a strong acid or strong base that is
added. This is precisely what the conjugate acid and base components of the
buffer do. Consider, for example, a buffer composed of acetic acid, HC2H302,
and acetate ion, C2H302, supplied by a salt such as NaC2H302. If we add extra
H+ to the buffer (from a strong acid) the acetate ion (the weak conjugate
base) can react with it as follows.
H+(aq) + C2H302 (aq) + HC2H2O2(aq) Thus, the added H+ changes
some of the buffer's Brønsted base, C H202, to its conjugate (weak) acid,
HC2H302. This reaction prevents a large buildup of H+ and a corresponding
decrease in pH that would otherwise be caused by the addition of
the strong acid.
A similar response occurs when a strong base is added to the buffer. The OH from
the strong base will react with some HC2H2O2.
HC2H2O2(aq) + OH-(aq) + C2H302 (aq) + H2O Here the added OH- changes some
of the buffer's Brønsted acid, HC H2O2, into its conjugate base, C2H302 .
This prevents a buildup of OH®, which would otherwise cause
17.7 | Buffer Solutions 799

a large increase in the pH. Thus, one member of a buffer team

neutralizes H+ that might get into the solution, and the other member
neutralizes OH-. Understanding buffers is an important tool for chemists to
use in applications ranging from the protocols of a research project
to designing a consumer product.

Practice Exercises
17.32 | Acetic acid, HC,H,O, and sodium acetate, NaC,H,O, (this
provides the ace tate ion C2H302 ), can be used to make an “acetate”
buffer. Does the acetate ion or the acetic acid increase when a strong
acid is added to the buffer? Is it the acetate ion or acetic acid that decreases
when a strong base is added to the buffer? Explain your answers. (Hint: Which of the
buffer components will react with HCl? Which will react with NaOH?)
17.33 | For a buffer composed of NH3 and NH4+ (from NH_CI),
write chemical equa tions that show what happens when (a) a
small amount of strong acid is added, and (b) a small amount of
strong base is added.

Calculating the pH of a Buffer Solution Calculating the pH

of a buffer mixture follows the same procedures we employed in Section
17.5 with a few small changes. The following example illustrates the
principles involved.

Example 17.6 Calculating the pH of a

Buffer
To study the effects of a weakly acidic medium on the rate of
corrosion of a metal alloy, a student prepared a buffer solution containing
both 0.110 M NaC2H30, and 0.090 M HC2H2O2. What is the pH of this
solution?
Analysis: We recognize that this is a buffer solution because it
contains both the weak acid HC2H2O2 and its conjugate base C2H302 .
Also, earlier we noted that when both solute species are present we
can use either K or Kí, to perform calculations, whichever is
handy.
Assembling the Tools: In our tables we find K, = 1.8 x 10-5 for HC
H30, so the simplest approach is to use K, and the corresponding
balanced chemical equation for the ionization of the acid.
[H+][C,H30) ,
HC,H,O = Ht+C2H30, Ấa =
= 1.8 x 10-5 IHC,H,0,1

We will also be able to use the simplifying approximations

developed earlier; these almost always work for buffers.
Solution: As usual, we begin with the chemical equation and
the expression for K, that we wrote above. Next, let's set up the
concentration table so we can proceed logically. We will take the
initial concentrations of HC2H2O2 and C2H2O2 to be the values
given in the problem. There's no H+ present from a strong acid, so
we set this concentration equal to zero. If the initial concentration of H+
is zero, its concentration must increase on the way to equilibrium, so
under H+ in the change row we enter +x. The other changes follow from
that. For buffer solutions the quantity x will be very small, so it is safe to
make the simplifying approximations in the last row. Here's the
completed table.
HC2H302 = H+ + C2H302
Initial concentrations (M)
0.090
0
0.
11 Changes in concentrations (M)
-X
+x
+
x Equilibrium concentrations (M) (0.090 – x)
(0.11 + x) 0.090
~0.11
800
Chapter 17 | Acid-Base Equilibria in Aqueous
Solutions

What remains, then, is to substitute the quantities from the last row of the table into the K,
expression.

(x)(0.11 +
x) (0.090 –
x)
(x)(0.11)
_
1 = 1.8 x 10-5 (0.090)

Solving for x
gives us

x=
(0.090) x 1.8 x 10-5
- (0.11)
= 1.5 x 10-5
 Because x equals [H+], we now have [H+] = 1.5 x 10-5 M.
Then we calculate pH:
pH = -log (1.5 x 10-5) = 4.82 Thus, the pH of
the buffer is 4.82.
Is the Answer Reasonable? Again, we check our assumptions and find they worked
(0.090 – 0.000015 = 0.090 and 0.11 + 0.000015 = 0.11). Also, we can check
the answer in the usual way by substituting our calculated equilibrium
values into the mass action expression. Let's do it.
Notice how small x is
compared to the initial
concentrations. The simplification
was valid.

[H+][C2H302) _ (1.5 x 10-5)

(0.11)_ ,
[HC2H302] (0.090)
1) = 1.8 x
10-5

The reaction quotient equals K, so the values we've obtained are correct
equilibrium concentrations.

Practice Exercises
17.34 Calculate the pH of the buffer solution in the preceding example by using the K for
CH202. Be sure to write the chemical equation for the equilibrium as the
reaction of C,H,O2 with water. Then use the chemical equation as
a guide in setting up the equi librium expression for K. (Hint: If you
work the problem correctly, you should obtain the same answer as above.)
17.35 One liter of buffer is made by dissolving 100.0 grams of
acetic acid, HC,H302, and 100.0 grams of sodium acetate,
NaC2H302, in enough water to make one liter. What is the pH of this
solution?

The "Common lon Effect” If the solution in the preceding example had contained only acetic acid with
a concentra tion of 0.090 M, the calculated [H+] would have been 1.3 x 10-3 M,
considerably higher than that of the buffer, which also contains 0.11
 MCH302 . The effect of adding sodium acetate, a substance
containing C2H2O2 ion, to a solution of acetic acid is to suppress the
ionization of the acid—it's an example of Le Châtelier's principle. Suppose, for
example, we had established the equilibrium

HC H302
H+ +
C2H302

According to Le Châtelier's principle, if we add C H202, the reaction will

proceed in a direction to remove some of it. This will shift the
equilibrium to the left, thereby reducing the concentration of H+.
In this example, acetate ion is said to be a common ion, in the sense that it is common to
both the acetic acid equilibrium and to the salt we added, sodium
acetate. The suppression of the ionization of acetic acid by addition of the
common ion is referred to as the common ion effect. We will encounter this
phenomenon again in Chapter 18 when we consider the solubilities of
salts.
17.7 | Buffer Solutions 801

Simplifications in Buffer Calculations

There are two useful simplifications that we can use in working buffer calculations. The
first is the one we made in Example 17.3:

Because the initial concentrations are so close to the equilibrium concentrations in the buffer mixture, we
can use initial concentrations of both the weak acid and its conjugate base as though they were equilibrium
values.
There are some buffer systems for which these simplifications might not work. However, you will not encounter them
in this text.

A further simplification can be made because the mass action expression

contains the ratio of the molar concentrations (in units of moles per liter) of the acid and
conjugate base. Let's enter these units for the acid and its conjugate base into the
mass action expres sion. For an acid HA,

K – [H+][A-] – [H+](mol A ) – [H+](mol A-)

[HA] (mol HA 1) (mol HA)
(17.16)

Notice that the units L-1 cancel from the numerator and denominator. This
means that for a given acid-base pair, [H+] is determined by the mole ratio of
conjugate base to conjugate acid; we don't have to use molar concentrations.

For buffer solutions only, we can use either molar concentrations or moles in the ka (or K)
expression to express the amounts of the acid and its conjugate base. However, we must use the
same units for each member of the pair.

A further consequence of the relationship derived in Equation 17.16 is that the pH

of a buffer should not change if the buffer is diluted. Dilution changes the volume
of a solu tion but it does not change the number of moles of the solutes, so their
mole ratio remains constant and so does (H+).

Preparing Buffers with a Desired pH The hydrogen ion concentration

of a buffer is controlled by both K, and the ratio of con centrations (or ratio of
moles) of the members of the acid-base pair. This can be seen by rearranging
Equation 17.16 to solve for [H+]:

[H+]= K HA
(17.17)
[A
]

or

[H+] = K mol HA
mol A
(17.18)

Solutions of conjugate acid-base pairs will generally act as buffers

when the mole (or molarity) ratio of acid to base is between 0.1 and 10. When this
ratio is less than 0.1, added base will cause large pH changes. When the ratio is greater
than 10, small addi tions of acid will cause large pH changes. When the ratio is close to
1.0, the solution will be effective if either strong acid or strong base is added. Therefore,
if we want to prepare a buffer that works well near some specified pH, we look for an
acid with a K, as close to the desired pH as possible. A high concentration of both the
conjugate acid and base will increase the buffer's ability to resist pH change. This
is called the buffer capacity, and it is equal to the moles of strong acid, or strong
base, needed to change the pH of one liter of buffer by 1.0 pH unit. For experiments
 in biology, the toxicity of the members of the acid-base pair must also be considered,
and that often narrows the choices considerably.
802
Chapter 17 Acid-Base Equilibria in Aqueous
Solutions

Example 17.7 Preparing a Buffer Solution to Have a

Predetermined pH
A solution buffered at a pH of 5.00 is needed in an experiment. Can we use acetic acid and sodium
acetate to make it? If so, what is the mole ratio of acetic acid and sodium
acetate that will result in a pH= 5.00 solution? How many moles of
NaC2H302 must be added to 1.0 L of a solution that contains 1.0 mol
HC2H2O2 to prepare the buffer?
Analysis: We need to do three things in this problem. First, we need to decide if, in
fact, acetic acid can be used for a pH= 5.00 buffer. Second, we need to
use the appropri ate equations to determine the mole ratio and then, third,
the amount of sodium acetate to use.
Assembling the Tools: The first tool describes the necessary relationship between pK,
and pH to successfully prepare a buffer solution:
pH = pK, +1 If we only have the K, we also need Equation 17.6 to
calculate the pK. Next we need the equations to convert pH to [H+) and
then use it to solve Equation 17.16 to calculate the necessary mole
ratio. Once we have this, we can proceed to calculate the number of
moles of C2H30, needed, and then the number of moles of NaC
H202.
Solution: Looking up the K for acetic acid we find it is 1.8 x 10-5. Because we want the pH to be
5.00, the pK, of the selected acid should be 5.00 + 1. We use
Equation 17.6 to calculate the pK.
PK, = -log(1.8 x 10-5) = 4.74 From this we determine
that acetic acid is appropriate for this buffer.
Next, we use Equation 17.16 to find the mole ratio of
solutes.

(mol HC H302) [H+] = K, X

(mol C H20,-)

First, let's solve for the mole

 ratio.

(mol HC2H302)_[H+]
(mol C2H202) K

The desired pH = 5.00, so [H+] = 1.0 x 10-; also K = 1.8 x 10-5.

Substituting gives
(mol HC2H302)
(mol C2H302)
1.0 x 10-5 1.8
x 10-5

This is the mole ratio of the buffer components that is

needed.
For the final step, the solution we are preparing contains 1.0 mol HC2H2O2, so the number
of moles of acetate ion required is
moles C H20,-- 1.0 mol HC,H,O,
13

0.56 = 1.8 mol

CH302
For each mole of NaC H30, there is one mole of C2H302 , so to prepare the solution we need 1.8
mol NaC H202. . Are the Answers Reasonable? A 1-to-1 mole ratio of
C,H,O, to HC2H30, would give pH = pk = 4.74. The desired pH of 5.00 is
slightly more basic than 4.74, so can expect that the amount of conjugate
base needed should be larger than the amount of conjugate acid. Our
answer of 1.8 mol of NaC,H,O2 appears to be reasonable.
17.7 | Buffer Solutions 803

Practice Exercises
17.36 From Table 17.2 select an acid that, along with its sodium salt, can
be used to make a buffer that has a pH of 5.25. If you have 500.0 mL of a
0.200 M solution of that acid, how many grams of the corresponding
sodium salt do you have to dissolve to obtain the desired pH? (Hint: There is
more than one correct answer to this problem. The first step is to determine the
ratio of molarities of the conjugate acid and conjugate base.)
17.37 A chemist needed an aqueous buffer with a pH of 3.90.
Would formic acid and its salt, sodium formate, make a good pair for this
purpose? If so, what mole ratio of the acid, HCHO2, to the anion of this
salt, CHO, , is needed? How many grams of NaCHO2 would have to be
added to a solution that contains 0.10 mol HCHOZ?

If you take a biology course, you're likely to run into a logarithmic form of
Equation 17.9 called the Henderson-Hasselbalch equation. This is
obtained by taking the negative logarithm of both sides of Equation 17.9 and
rearranging to get

pH = pk + log [A-]
(17.19)

In most buffers used in the life sciences, the anion A comes from a salt in which
the cation has a charge of 1+, such as NaA, and the acid is monoprotic. With
these as conditions, the equation is sometimes written

pH = pk + log (salt)
(17.20)
(acid]

For practice, you may wish to apply this equation to buffer

problems at the end of the chapter.

Calculating pH Change for a Buffer Earlier we described how a

buffer is able to neutralize small amounts of either strong acid or base
to keep the pH from changing by large amounts. We can use this knowledge now
to calculate how much the pH will change.

Example 17.8 Calculating

How a Buffer Resists Changes in pH
How much will the pH change if 0.020 mol of HCl is added to a
buffer solution that was made by dissolving 0.12 mol of NH3 and 0.095 mol of
NH4Cl in 250 mL of water?
Analysis: This problem will require two calculations. The first is to
determine the pH of the original buffer. The second is to determine the pH
of the mixture after the HCl has been added. For the second calculation, we
have to determine how the acid changes the amounts of NH3 and NH4+.
Assembling the Tools: For the pH of the initial solution we need
the chemical reaction and the K for NH3.
[NH ][OH-] NH3 + H2O =
NH+ + OH- K= ! On )= 1.8 x 10-5
 [NH3]

To determine the pH of the solution after the HCI was added we

need the chemical reaction for HCl in this mixture. Since HCl is a strong
acid, it will react quantitatively (completely) with the conjugate base of
the buffer—in this case, NHz. The balanced molecular equation is
NH, + HCl – NHẠC
804
Chapter 17
Acid-Base Equilibria in Aqueous Solutions

In this case it is better to write the net ionic equation as

NH3 + H+ NH4+ We then do a limiting reactant calculation to determine how

much of the NH3 will be con verted to NH4+. We then use the new amounts of
NH3 and NH4+ to determine the pH.
Solution: We begin by calculating the pH of the buffer before the HCl is added.
The solution contains 0.12 mol of NH3 and 0.095 mol of NH4+ from the complete
dissocia tion of the salt NH_Cl. We can enter these quantities into the mass
action expression in place of concentrations and solve for [OH-]. As noted earlier,
we can use moles of NH3 and NH4in place of molarities to solve buffer problems.
5 (mol NH4+) x [OH-] (0.095)[OH-1
(mol NH3)
(0.12)
The solution also contains 0.095 mol of Cl-, of course, but this ion is not involved in the equilibrium.

1.8 x 10-5 – (mol NH4+) X (OH-1

solving for [OH-] gives

[OH-] = 2.3 x 10-5 To calculate the pH, we obtain pOH and subtract it from
14.00.
pOH = -log (2.3 x 10-5) = 4.64
pH = 14.00 – 4.64 = 9.36 This is the pH before we add any HCl.
Next, we consider the reaction that takes place when we add the HCl to the
buffer. The 0.020 mol of HCl is completely ionized, so we're adding 0.020 mol H+. The
0.020 mol of acid will react with 0.020 mol of NH, to form 0.020 mol of NH4+. This
causes the number of moles of NH3 to decrease by 0.020 mol and the number of moles
of NH + to increase by 0.020 mol. After addition of the acid, we have
The equilibrium constant for this reaction is 1.8 x 1010, so the reaction goes almost to completion. Nearly all
the added H+ reacts with NH3.
Number of moles
in the original buffer mixture
Change in the number of moles because of reaction

moles of NH3 = 0.12 mol – 0.020 mol = 0.10 mol NH3 moles of NH4+ = 0.095 mol +
0.020 mol = 0.115 mol NH4+

We now use these new amounts of NH3 and NH4+ to calculate the new pH of
the buffer solution. First, we calculate [OH-].
(mol NH4+) X (OH-] 1.8 x 10-5 = 1
(0.115)[OH-] (mol NH3)
(0.10)

Solving for [OH-] gives

[OH-] = 1.6 x 10-5 To calculate the pH, we obtain pOH and subtract it from 14.00.
pOH = -log (1.6 x 10-5) = 4.80
pH = 14.00 – 4.80 = 9.20 This is the pH after addition of the acid. We're
asked for the change in pH, so we take the difference between the two
values:
change in pH = 9.20 – 9.36 = -0.16 Thus, the pH has decreased by 0.16 pH
units.
Is the Answer Reasonable? In general, we can assume that changes in pH
should be small (less than 1.0 pH unit), otherwise there's no simple way to estimate
how much the