CHAPTER

15
Complex Acid/Base Systems
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 15A MIXTURES OF STRONG AND WEAK ACIDS
OR STRONG AND WEAK BASES

EXAMPLE 15-1
Calculate the pH of a mixture that is 0.1200 M in hydrochloric a
cid and 0.0800 M in the weak acid HA (Ka=1.00×10-4) during
its titration with 0.1000 M KOH. Compute results for additio
ns of the following volumes of base: (a) 0.00 mL and (b) 5.00
mL. (V0 = 25 mL)

(a) 0.00 mL KOH Added

In the presence of the two acids, however, we can be certain t
hat the concentration of hydronium ions from the dissociation
of water is extremely small.

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 Note that [A] is equal to the concentration of hydroniu
m ions from the dissociation of HA.
Now assume that the presence of the strong acid so re
presses the dissociation of HA that [A] 0.1200 M; the
n

To check this assumption,

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 We see that [A] is indeed much smaller than 0.1200 M
, as assumed.
(b) After Adding 5.00 mL of Base

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 and we may write

To determine whether our assumption is still valid, the

concentration of HA is now 0.0800 × 25.00/30.00 = 0.
0667, and find

which is still much smaller than 0.0833.

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 EXAMPLE 15-2
Calculate the pH of the solution that results when 29.0
0 mL of 0.1000 M NaOH is added to 25.00 mL of the
solution described in Example 15-1.

Clearly, [A-] is no longer much smaller than [H3O+], a

nd we must write

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 In addition, from mass-balance considerations, we
know that

the acid dissociation-constant expression for HA and

obtain

Substitution of this expression into Equation 15-2

yields
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 Substitution for [A-] and cHCl in Equation 15-1 yields

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 Collecting terms gives

Solving the quadratic equation gives

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 When the amount of base added is equivalent to the amount of
hydrochloric acid originally present, the solution is identical
in all respects to one prepared by dissolving appropriate
quantities of the weak acid and sodium chloride in a suitable
volume of water.

The sodium chloride, however, has no effect on the pH; thus,

the remainder of the titration curve is identical to that for a
dilute solution of HA.

Figure 15-1 depicts the pH changes that occur during the

titration of mixtures containing hydrochloric acid and several
weak acids.

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 Figure 15-1
Curves for the titration
of strong acid/weak aci
d mixtures with 0.1000
M NaOH. Each titratio
n is on 25.00 mL of a s
olution that is 0.1200
M in HCl and 0.0800
M in HA

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 Note that the rise in pH at the first equivalence point is
small or essentially nonexistent when the weak acid
has a relatively large dissociation constant.

For weak acids of intermediate strength (Ka somewhat

less than 10-4 but greater than 10-8), there are usually
two useful end points.

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 15B POLYFUNCTIONAL ACIDS AND BASES

15B-1 The Phosphoric Acid System

Phosphoric acid is a typical polyfunctional acid. In aq
ueous solution, it undergoes the following three dissoc
iation reactions:

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 With this acid, as with other polyprotic acids, Ka1 ＞ Ka
2 ＞ Ka3.

For the first two dissociation equilibria for H3PO4, we

write

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 Similarly, for the reaction

we may write

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15B-2 The Carbon Dioxide Carbonic Acid System

Similarly, for the reaction

a more useful way of discussing the acidity of solutions

of carbon dioxide is to combine Equation 15-3 and 15-4
to give
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 Similarly, for the reaction

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 EXAMPLE 15-3
Calculate the pH of a solution that is 0.02500 M CO2.
From mass-balance considerations,

The small magnitude of Khyd, K1, and K2 (see Equation

s 15-3, 15-4, and 15-5) suggests that

and we may write

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 From charge-balance considerations,

We will then assume

Thus,

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 Substituting these approximations into Equation 15-6
leads to

Calculated tentative values for [H2CO3], [CO ], and

[OH] indicate that the assumptions were valid.

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 15C BUFFER SOLUTIONS INVOLVING
POLYPROTIC ACIDS

Two buffer systems can be prepared from a weak diba

sic acid and its salts.

The first consists of free acid H2A and its conjugate ba

se NaHA,

and the second makes use of the acid NaHA and its co
njugate base Na2A.

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 EXAMPLE 15-4

Calculate the hydronium ion concentration for a buffer solution t

hat is 2.00 M in phosphoric acid and 1.50 M in potassium dihyd
rogen phosphate.

The principal equilibrium in this solution is the dissociation of

H3PO4.

We assume that the dissociation of H2PO4- is negligible; that is,

[HPO42- ] and [PO43- ] [H2PO4- ] and [H3PO4]. Then,

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 We now use the equilibrium-constant expression for
Ka2 to show that [HPO42- ] can be neglected:

and our assumption is valid.

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 For a buffer prepared from NaHA and Na2A, the secon
d dissociation will ordinarily predominate, and the equ
ilibrium is disregarded.

EXAMPLE 15-5
Calculate the hydronium ion concentration of a buffer
that is 0.0500 M in potassium hydrogen phthalate (KH
P) and 0.150 M in potassium phthalate (K2P).

Provided that the concentration of H2P in this solution

is negligible,
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 To check the first assumption, an approximate value for
[H2P] is calculated by substituting numerical values for
[H3O-] and [HP-] into the expression for Ka1:

This result justifies the assumption that [H 2P] ＜ ＜ [H

P] and [P2-].

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15D CALCULATION OF THE pH OF SOLUTIONS OF NaHA

Salts that are amphiprotic. Such salts are formed durin

g neutralization titration of polyfunctional acids and b
ases.
When 1 mol of NaOH is added to a solution containin
g 1 mol of the acid H2A, 1 mol of NaHA is formed. Th
e pH of this solution is determined by two equilibria e
stablished between HA and water:

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 We first write a mass-balance expression. That is,

The charge-balance equation takes the form:

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 The ion-product constant for water serves :

We first subtract the mass-balance equation from the

charge-balance equation.

We then rearrange the acid-dissociation constant

expressions for H2A to obtain

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 and for HA- to give

Substituting these expressions and the expression for

Kw into Equation 15-12 yields

Multiplying through by [H3O+] gives

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 We collect terms to obtain

Finally, this equation rearranges to

We can make the approximation that

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 Introduction of this relationship into Equation 15-13 g
ives

Frequently, the ratio cNaHA/Ka1 is much larger than

unity in the denominator of Equation 15-15, and Ka2c
NaHA is considerably greater than Kw in the numerat
or. The equation simplifies to

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EXAMPLE 15-6

Calculate the hydronium ion concentration of a 1.00×10-3M N

a2HPO4 solution.

The pertinent dissociation constants are Ka2 and Ka3, which

both contain [HP42- ]. Their values are Ka2=6.32×10-8 and K
a3=4.5×10 . Considering again the assumptions that led to
-13

Equation 15-16, we find that (1.0×10-3)/(6.32× 10-8) is muc

h larger than 1, so that the denominator can be simplified.
The product Ka2cNa2HPO4 is by no means much larger than Kw
, however. We therefore use a partially simplified version o
f Equation 15-15:

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 Use of Equation 15-16 yields a value of 1.7x10-10 M.

EXAMPLE 15-8
Calculate the hydronium ion concentration of a 0.100
M NaHCO3 solution.We assume, as we have earlier (p
age 353), that [H2CO3]<<[CO2(aq)] and that the follo
wing equilibria describe the system adequately:

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 Clearly, cNaHA/Ka1 in the denominator of Equation 15-15
is much larger than unity; in addition, Ka2cNaHA has a value
of 4.69x10-12, which is substantially greater than Kw. Thus,
Equation 15-16 applies, and

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 15E TITRATION CURVES FOR
POLYFUNCTIONAL ACIDS
Compounds with two or more acid functional groups yield mu
ltiple end points in a titration provided that the functional grou
ps differ sufficiently in strength as acids.

Figure 15-2 shows the titration curve for a diprotic acid H2A w
ith dissociation constants of Ka1=1.00×10-3 and Ka2 ＝ 1.00 ×1
0-7.

to obtain the initial pH (point A), we treat the system as if it co

ntained a single monoprotic acid with a dissociation constant o
f Ka1=1.00×10-3.

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 In region B, we have the equivalent of a simple buffer
solution consisting of the weak acid H2A and its conju
gate base NaHA.
At the first equivalence point (point C), we have a sol
ution of an acid salt and use Equation 15-15 or one of
its simplifications. In the region labeled D, we have a
second buffer consisting of a weak acid HA and its co
njugate base Na2A.

In the region labeled F, we compute the hydroxide con

centration from the molarity of the NaOH.

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 Figure 15-2
Titration of 20.00 mL of 0
.1000 M H2A with 0.1000
M NaOH.

For H2A,
Ka1=1.00×10-3 Ka2=1.00×1
0-7.

The method of pH calcula

tion is shown for several p
oints and regions on the tit
ration curve.

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EXAMPLE 15-9
Construct a curve for the titration of 25.00 mL of 0.1000
M maleic acid, HOOC-CH=CH-COOH, with 0.1000 M N
aOH.
Symbolizing the acid as H2M, we can write the two dissoci
ation equilibria as

Because the ratio Ka1/Ka2 is large (2×104), we proceed as ju

st described.

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Initial pH
Only the first dissociation makes an appreciable contribution
to [H3O+]; thus,

Mass balance requires that

Substituting these relationships into the expression for Ka1

gives

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Rearranging yields

Because Ka1 for maleic acid is large, we must solve the quadratic
equation exactly or by successive approximations. When we do s
o, we obtain

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First Buffer Region
The addition of 5.00 mL of base results in the formation of a
buffer consisting of the weak acid H2M and its conjugate base
HM-.

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The approximation that [OH-] is very small. Substitution of
these expressions into the dissociation constant relationship
gives

Additional points in the first buffer region can be computed in

a similar way.

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 Just Prior to First Equivalence Point
For example, at 24.90 mL of NaOH added,

Mass balance gives

Charge balance gives

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 we can neglect [OH-] in the previous equation and can
replace [Na+] with cNaHM. After rearranging, we obtain

Substituting this into the mass-balance expression and

solving for [H3O+] gives

If we express [M2-] and [H2M] in terms of [HM-] and

[H3O+], the result is

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 Multiplying through by [H3O] gives, after rearrangem
ent,

Substituting [HM]≈4.99×10-2, cHM=2.00×10-4, and the

values for Ka1 and Ka2 leads to

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 The solution for this equation is

The same reasoning applies at 24.99 mL of titratant, w

here we find

First Equivalence Point

At the first equivalence point,

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 Our simplification of the numerator in Equation 15-15 is
clearly justified. On the other hand, the second term in
the denominator is not 1. So,

Just after the First Equivalence Point

Until the second equivalence point, we can obtain the
analytical concentration of HM- and M2- from the
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 titration stoichiometry. At 25.01 mL, the values are calcula
ted as

the mass balance is

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 and the charge balance is

Again, the solution should be acidic, and so we can

neglect OH as an important species.

Subtracting the mass balance from the charge balance

and solving for [H3O+] gives

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歐亞書局
 Second Buffer Region
Further additions of base to the solution create a new
buffer system consisting of HM- and M2-. When we int
roduce 25.50 mL of NaOH, for example,

and the molar concentration of NaHM is

Substituting these values into the expression for Ka2 gi

ves

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 The assumption that [H3O+] is small relative to c and c is
valid, and pH 4.54.
Just Prior to Second Equivalence Point
At 49.90 mL, cHM-=1.33510-4 and cM2- = 0.03324. The pr
imary equilibrium is now

We can write the equilibrium constant as

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 It is easier to solve for [OH-] than for [H3O+]. This
gives

and

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 For 49.99 mL, which leads to [OH-]=1.80×10-5 M and
pH 9.26.
Second Equivalence Point
After the addition of 50.00 mL of 0.1000 M sodium h
ydroxide, the solution is 0.0333 M in Na2M.

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 pH Just Beyond the Second Equivalence Point
In the region just beyond the second equivalence point
(50.01 mL, for example),

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 The [OH-] now comes from the reaction of M2 with w
ater and from the excess OH- added as titrant.

It is now relatively easy to solve for [HM-] from Kb1.

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 The same reasoning applies to 50.10 mL, where the ca
lculations give
pH beyond the second equivalence point

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 Figure 15-4 shows titration curves for three other polyprotic
acids. These curves illustrate that a well-defined end point c
orresponding to the first equivalence point is observed only
when the degree of dissociation of the two acids is sufficient
ly different.

The ratio of Ka1 to Ka2 for oxalic acid (curve B) is approximat

ely 1000.

The second end point provides a means for the accurate dete
rmination of oxalic acid.

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 Figure 15-4
Curves for the titration o
f polyprotic acids.
A 0.1000 M NaOH solut
ion is used to titrate 25.
00 ML of 0.1000 M H3P
O4(curve A),

0.1000 M oxalic acid (c

urve B),

0.1000 M H2SO4
(curve C).

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 Curve A in Figure 15-4 is the theoretical titration curv
e for triprotic phosphoric acid. Here, the ratio Ka1/Ka2 i
s approximately 105, as is Ka2/Ka3.

Curve C is the titration curve for sulfuric acid, a subst

ance that has one fully dissociated proton and one that
is dissociated to a relatively large extent (Ka2 =1.021
0-2), only a single end point.

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FEATURE 15-1

The Dissociation of Sulfuric Acid

Sulfuric acid is unusual in that one of its protons
behaves as a strong acid and the other as a weak acid
(Ka2 =1.02×10-2). Ion concentration of sulfuric acid
solutions is 0.0400 M solution.

The expression for Ka2 reveals that

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 Clearly, [SO42- ] is not small relative to [HSO4-]. From s
toichiometric considerations, it is necessary that

Rearrangement yields

Mass-balance considerations require that

Combining the last two equations and rearranging yield

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 Introduction of these equations for [SO42- ] and [HSO4-
] into the expression for Ka2 yields

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 15F TITRATION CURVES FOR
POLYFUNCTIONAL BASES
To illustrate, consider the titration of a sodium
carbonate solution with standard hydrochloric acid.
The important equilibrium constants are

Figure 15-5 illustrates that two end points are

observed in the titration of sodium carbonate, the
second being appreciably sharper than the first.

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 Figure 15-5
Curve for the titration of
25.00 mL of 0.1000 M
Na2CO3 with 0.1000 M
HCl.

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 15G TITRATION CURVES FOR
AMPHIPROTIC SPECIES
an amphiprotic substance, when dissolved in a suitable solve
nt, behaves both as a weak acid and as a weak base.
For example, in sodium dihydrogen phosphate solution, the
principal equilibria are:

Kb3 is much too small to permit titration of H2PO4- with an a

cid, but Ka2 is large enough for a successful titration of the io
n with a standard base solution.

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 For which the analogous equilibria are:

The magnitude of the constants indicates that HPO42- c

an be titrated with standard acid but not with standard
base.

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 FEATURE 15-2

Acid/Base Behavior of Amino Acids

The simple amino acids are an important class of amp
hiprotic compounds that contain both a weak acid and
a weak base functional group. In an aqueous solution
of a typical amino acid, such as glycine, three importa
nt equilibria operate:

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 The reaction one would observe between a carboxylic
acid and an amine:

The amino acid species in Equation 15-17, which bear

s both a positive and a negative charge, is called a zwi
tterion.

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 The pH at which no net migration occurs is called the
isoelectric point and is an important physical constant
for characterizing amino acids. The isoelectric point is
readily related to the ionization constants for the speci
es. Thus, for glycine,

At the isoelectric point,

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 we obtain for the isoelectric point

Substitution of Kw/[H3O+] for [OH-] and rearrangemen

t yield

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 The isoelectric point for glycine occurs at a pH of 6.0,
as shown by the following:

Addition of formaldehyde removes the amine function

al group, however, and leaves the carboxylic acid avai
lable for titration with a standard base. For example, w
ith glycine,

The titration curve for the product is that of a typical c

arboxylic acid.

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 15H THE COMPOSITION OF SOLUTIONS OF A
POLYPROTIC ACID AS A FUNCTION OF pH
For example, if we let cT be the sum of the molar concentr
ations of the maleate-containing species in the solution th
roughout the titration described in Example 15-9, the alph
a value for the free acid α0 is defined as

Where

Alpha values for HM- and M2- are given by similar equati
ons:
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歐亞書局 p.373
歐亞書局
 FEATURE 15-3
A General Expression for Alpha Values
For the weak acid HnA, the denominator in all alpha v
alue expressions takes the form:

The numerator for a0 is the first term in the denominat

or; for a1, it is the second term, and so forth. Thus, if
we let D be the denominator,
and

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 The three curves plotted in Figure 15-6 show the alpha
values for each maleatecontaining species as a functio
n of pH.
The solid curves in Figure 15-7 depict the same alpha
values but now plotted as a function of volume of sodi
um hydroxide as the acid is titrated.

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 Figure 15-6
Composition of H2M
solutions as a
function of pH.

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 Figure 15-7
Titration of
25.00 mL of
0.1000 M maleic acid
with 0.1000 M NaOH.

The solid curves are p

lots of alpha values a
s a function of volume
.

The broken curve is a

plot of pH as a functio
n of volume.

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 FEATURE 15-4
Logarithmic Concentration Diagrams
Logarithmic concentration diagrams can be obtained fr
om the concentration of acid and the dissociation const
ants.
The diagram shown in Figure 15F-1 is a logarithmic c
oncentration diagram for a maleic acid concentration o
f 0.10 M.
The changes in slope in the diagram for the maleic aci
d species occur near what are termed system points.

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 For maleic acid, the first system point occurs at log cT
＝ － 1 and pH ＝ pKa1 ＝ － log (1.30×10-2) ＝ 1.
89, while the second system point is at pH ＝ pKa2 ＝
－ log (5.90×10-7) 6.23 and log cT ＝－ 1.

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