In the Classroom
Predicting Acid–Base Titration Curves without Calculations
Dennis Barnum
Department of Chemistry, Portland State University, P.O. Box 751, Portland, OR 97207-0751; barnumd@pdx.edu
A common approach to teaching acid–base chemistry is
to have students calculate titration curves. Students often
concentrate on setting up the equations or the spreadsheet,
and they either lose sight of or fail to recognize the general
principles that the calculations are intended to convey. Teach-
ing students how to make a qualitative sketch of the expected
titration curve helps to focus attention on the general principles.
In this paper a simple qualitative system for sketching
all manner of acid–base titration curves is described. Lengthy
calculations, complicated algebraic equations, and computers are
avoided altogether. All situations are handled with equal ease,
including polyprotic acids, polyprotic bases, salts, and mixtures
of salts with acids or bases. The only information required is
approximate values of the acid or base ionization constants. No
new principles are involved. Persons already familiar with acid–
base titration curves will find the method obvious. It is presented
as a teaching tool and a method to help students tie the several
special cases together into a single comprehensive presentation.
A qualitative approach takes advantage of the following
well-known facts about acid base equilibria:
1. Acid–base reactions are rapid and reversible.
2. When titrating a weak acid with strong base the pH at
the half-equivalence point is equal to the pK a of the acid:
pH1/2 = pK a; 2 < pK a < 12 (1)
3. When titrating a weak base with a strong acid the pOH
at the half-equivalence point is equal to pK b of the base:
pOH1/2 = pK b; 2 < pK b < 12 (2)
In either case, acid or base, the half-equivalence point is
the middle of the buffer region. Consequently, the titration
curve must be nearly flat at this point, sloping slightly upward
if the titrant is a base or slightly downward if the titrant is
an acid. By examining a few real or calculated titration curves
one can get a good qualitative feeling for the slope. Alterna-
tively, one can make use of Sturrock’s observation that for a
monoprotic acid or base the pH changes by about one unit
between 25% and 75% of the volume required to reach the
equivalence point (1).
4. Beyond the equivalence point, in the region where ex-
cess titrant is being added, the pH must approach the
pH of the titrant.
5. For monoprotic acids or bases, the pH at the equivalence
point is approximately halfway between the pH at the
half-equivalence point and either the upper or lower
limit established by the pH of the titrant. The equiva-
lence point is the steepest part of the titration curve.
Titration of a Weak Acid with a Strong Base
Figure 1 illustrates the qualitative approach using the
well-known titration of 0.100 M acetic acid with 0.100 M
sodium hydroxide as an example. For convenience, assume
that the initial volume of acid is 35.00 mL and that one is
938 Journal of Chemical Education • Vol. 76 No. 7 July 1999 • JChemEd.chem.wisc.edu
using a 50-mL buret.
Step 1. Calculate the volume of titrant required to reach
the equivalence point from the relationship
Vacid Macid = Vbase Mbase
In this case the equivalence point is calculated to be at 35.0 mL.
The volume at the half-equivalence point is therefore 17.5 mL.
Step 2. Since pKa of acetic acid is 4.76 the curve must pass
through pH = 4.76 at 17.5 mL. This is the middle of the
buffer region where the curve is nearly flat. Draw a short
segment of the curve through point B, nearly horizontal, but
sloping slightly upward as shown in Figure 1. For a rough
sketch of the titration curve it is adequate to make the slope
about the same as observed in other calculated or measured
titration curves. For a somewhat better approximation to the
slope the pH should increase by about one unit between the
25% point at 8.8 mL and the 75% point at 26.3 mL.
Step 3. Beyond the equivalence point, in the region of
excess titrant, the curve must approach the pH of the titrant.
The pH of 0.100 M NaOH is 13.0, so one draws a short
segment of the curve, well beyond the equivalence point,
nearly flat, approaching pH = 13.0. This is segment D in
Figure 1.
Step 4. The pH at the equivalence point is roughly half-
way between pH1/2 and the upper pH limit; in this case, about
halfway between 4.76 and 13.0, which is 8.9. At this pH the
curve has its steepest slope. Draw in a short segment, nearly
vertical, through pH 8.9 and 35.0 mL (point C in Fig. 1).
Step 5. The initial pH (point A in Fig. 1) can be esti-
mated by observing that addition of 0.100 M HCl to the
initial solution causes the pH to approach a lower limit equal to
the pH of 0.100 M HCl. Thus, the initial pH is approximately
halfway between 4.76 and pH 1.0; that is, at approximately
2.9. (This point is discussed further in a following section
on reversibility.)
Step 6. Complete the curve, as shown in Figure 1, by
connecting the heavily lined known segments.
Reversibility of Titration Curves
Figure 1 also illustrates the reversible nature of titration
curves. Note that the x-axis shows added 0.100 M NaOH
going from left to right in the usual manner, but also shows
added 0.100 M HCl going from right to left. For simplicity,
the concentrations of the HCl and NaOH are taken to be
equal. Because the acid–base reactions are reversible, one can
move in either direction along the curve depending on
whether NaOH or HCl is added.
For example, in the titration of acetic acid with base one
starts at point A. As 0.100 M NaOH is added the curve
progresses from left to right through points B, C, and D. If
the analyst stops adding base at any point and starts adding
acid instead, the same curve is traced backward, from right

to left. There is, of course, some dilution due to added titrant
but the dilution effect is small and can be ignored when one
is interested only in the qualitative features of the curve.
One might also start at point A and add 0.100 M HCl
instead of base. In this case the analyst is just adding HCl to
a solution of acetic acid and the titration curve simply starts
at point A and approaches pH = 1.0, which is the lowest the
pH can possibly go owing to addition of 0.100 M HCl.
Because the curve is reversible, Figure 1 also contains the
titration curve for an acetate salt titrated with an acid. The
solution at point C is exactly the same as a solution prepared
by dissolving solid sodium acetate in water. Thus, titration
of an acetate salt with an acid starts at point C and progresses
from right to left giving an equivalence point at point A. The
half-equivalence point at B occurs at pOH1/2 = pKb for the
acetate ion, which, of course, is the same as pH1/2 = pKa for
the conjugate acid of acetate ion.
Titration of Polyprotic Acids
Titrating a polyprotic acid is the same as titrating an
equimolar mixture of two or more monoprotic acids having
different pKa values. The strongest acid is titrated first, followed
by the second strongest acid, then the third strongest, etc.
To illustrate, the curve for 15.0 mL of 0.100 M phosphoric
acid titrated with 0.100 M NaOH is developed in Figure 2.
For phosphoric acid we have pKa = 2.17, pKa = 7.21, and
1 2
pKa = 12.36. One can think of phosphoric acid as a mixture
3 point G and proceeds from right to left through points F, E,
of the three monoprotic acids H3PO4, H2PO4{, and HPO42{.
One would then expect equivalence points at 15.0, 30.0, and
45.0 mL. From zero to 15.0 mL, H 3PO4 is being converted
to H2PO4{ and the half-equivalence point occurs at 7.50 mL.
This is point B in Figure 2. The pH at this point is approxi-
Figure 1. Sketching a titration curve qualitatively for 35.0 mL of
0.100 M acetic acid titrated with 0.100 M sodium hydroxide.
Addition of 0.100 M NaOH progresses from left to right; addition
of 0.100 M HCl progresses from right to left. A is a solution of
acetic acid only, HOAc; B is the middle of the buffer region where
[HOAc] = [OAc {] and pH1/2 = pKa of acetic acid; C is a solution
of sodium acetate, NaOAc; D is the region of sodium acetate and
excess sodium hydroxide; and E represents a region of acetic acid
and excess HCl.
JChemEd.chem.wisc.edu • Vol. 76 No. 7 July 1999 • Journal of Chemical Education
In the Classroom
mately equal to pKa = 2.2. The solution at this point is a
1
buffer of H 3PO 4 and H2PO 4{, so one draws a nearly flat
segment of the curve at this point.
From 15.0 to 30.0 mL the second strongest acid, H2PO4{,
is being converted to HPO42{. A second half-equivalence
point therefore occurs at 22.5 mL and pH = 7.2, so one draws
a nearly flat segment of the curve through point D.
Finally, from 30.0 to 45.0 mL the third acid, HPO42{,
is being titrated. For this acid pKa = 12.36. But, recall that
1
the relation between pH1/2 and pKa is only valid in the range
approximately 2 to 12, so the curve passes a little lower than
12.4 at the third half-equivalence point at 37.5 mL. Draw a
short, nearly flat segment through point F. Also, draw a
segment well beyond the third equivalence point showing the
curve approaching the pH of the titrant.
After drawing segments through the half-equivalence
points, one can go back and locate the equivalence points.
Point C is approximately halfway on the vertical scale between
B (pH = 2.2) and D (pH = 7.2), that is, at about 4.7. The
second equivalence point, E, is approximately halfway between
D and F. At the third equivalence point the curve is essentially
flat. That is, the third proton of phosphoric acid is so weak
there is no discernible step at the third equivalence point.1
Because the titration curve is reversible, Figure 2 also
contains the curves for phosphate salts titrated with a strong
acid. Point G in Figure 2 represents a solution of Na3PO4.
Consequently, the titration of trisodium phosphate starts at
D, C, B, and A. Similarly, the titration of Na2HPO4 starts at
point E and gives an equivalence point at C. Because the three
acid ionization constants of phosphoric acid are fairly far
apart, two relatively steep equivalence points are observed.
We now ask, what happens when the acid ionization
constants are close together? Tartaric acid is a good example,
having pKa = 3.04 and pKa = 4.37. In Figure 3 the curve for
1 2
titration of 20.0 mL of 0.100 M tartaric acid with 0.100 M
NaOH is sketched. One expects equivalence points at 20.0 mL
and 40.0 mL. The first half-equivalence point is at 10.0 mL
and the second at 30.0 mL. Consequently, we draw one short,
nearly flat segment through the point 10.0 mL and pH 3.0
(point B) and a second through the point 30.0 mL and pH
4.4 (point D). The pH at the first equivalence point is
approximately halfway between 3.0 and 4.4; that is, about
3.8. Clearly, there is no room for a large “step” in pH at the
first equivalence point.
The pH at the second equivalence point is approximately
halfway between 4.4 and the upper limit of 13.0. Draw in a
short steep segment at 40.0 mL and pH 8.8 and a segment
approaching the pH of the titrant. Connect the known seg-
ments.
Amino Acids
Amino acids are a particularly interesting example of
polyprotic acids. We will take the titration of glutamic acid
as an example:
O O
HO C CH CH2 CH2 C OH
NH3
+
Cl-
Glutamic acid hydrochloride, H3glu+ Cl { ; p Ka 1 = 2.19
939
In the Classroom

O O
HO C CH CH2 CH2 C O-
+
NH3

Glutamic acid, H2glu; pKa 2 = 4.25

O O
-O C CH CH2 CH2 C O-
Na+
+
NH3

Glutamic acid monosodium salt, Hglu{ Na+; pK a 3 = 9.67

Acid ionization constants are counted from the most
highly protonated species; that is, from the hydrochloride,
in this case. We have:
pKa = 2.19 for ionization of the first –COOH group
1
Figure 2. Titration of 15.0 mL of 0.100 M phosphoric acid with
pKa = 4.25 for ionization of the second –COOH group
2
0.100 M NaOH. To cover the tip of the pH electrode, 15.0 mL of
pKa = 9.67 for ionization of the –NH3+ group
3 water was added at the start.
The titration of 15.0 mL of 0.100 M glutamic acid
hydrochloride with 0.100 M NaOH is shown in Figure 4.
Because there are three titratable protons we expect equivalence
points at 15.0, 30.0, and 45.0 mL. The curve must be relatively
flat as it passes through the middle of buffer regions with
pH = 2.2 at 7.5 mL, pH = 4.3 at 22.5 mL, and pH = 9.7 at
37.5 mL. The pH values at the three equivalence points are
approximately 3.3, 7.0, and 11.3.
Although Figure 4 is the titration curve for the hydro-
chloride salt of glutamic acid, it also contains the curve for
other forms. For example, if one were to start with glutamic
acid (rather than the hydrochloride) the curve would start at
point C and progress from left to right through D, E, F, and
G. Similarly, if one were to titrate the disodium salt with
strong acid the curve would start at point G and progress
from right to left.2

Titration of Salts and Weak Bases

Textbooks often treat the titration of salts such as sodium
acetate, trisodium phosphate, or potassium carbonate sepa- Figure 3. Titration of 20.0 mL of 0.100 M tartaric acid with 0.100 M
rately from neutral bases. This implies that the ions in salts NaOH. pKa 1 = 3.04; pKa 2 = 4.37.
are different from neutral weak bases such as ammonia or
ethylamine. However, if one compares ammonia with the
acetate ion it is seen that there is no difference:
NH3(aq) + H2O NH4+(aq) + OH{(aq)
CH3COO{(aq) + H2O CH 3COOH(aq) + OH{(aq)
Both equilibria are hydrolysis reactions and both represent
base ionization. In fact, most anions are bases and many are
strong enough that they can be analyzed by titration with
standard acid. 3 We have already seen that Figures 1 and 2
contain the titration curves for acetate and phosphate salts.
Values of base ionization constants of anions are not
commonly tabulated in textbooks.4 However, to sketch the
titration curve for an anion it is usually more convenient to
take the pH at the half-equivalence point to be equal to the
pKa of the conjugate acid of that base.

An Application: The Effect of Dilution on the Titration

of Weak Acids—an Apparent Paradox
As analyte and titrant are made more and more dilute, Figure 4. Titration of 15.0 mL of 0.100 M glutamic acid hydrochlo-
titrations become less feasible because the change in pH at the ride with 0.100 M NaOH. pKa 1 = 2.19; pKa 2 = 4.25; pKa 3 = 9.67.
equivalence point becomes smaller and less sharp. However,

940 Journal of Chemical Education • Vol. 76 No. 7 July 1999 • JChemEd.chem.wisc.edu


the behavior of weak acids is different from that of strong
acids, as one can see by comparing Figures 5 and 6. The curves
behave the same in the region of excess strong base. However,
in the region before the equivalence point the two figures
differ because of the requirement that the titration curve pass
through pH1/2 = pKa at the half-equivalence point.
Here is an apparent paradox. Even though the analytical
concentration of the weak acid is decreasing, the hydrogen ion
concentration remains nearly constant! The same phenomenon
is often seen in the general rule that the pH of a buffer is,
roughly, independent of dilution. How can the hydrogen ion
concentration (activity) remain constant when the concentra-
tion of the acid is decreased? The reason is that when a weak
acid or base is diluted the percentage ionized increases. Of course,
if the solution is made too dilute the relation pH1/2 = pKa
fails because approximations made in its derivation are no
longer valid. In Figure 6 one can see that for acetic acid the
relation is valid in the range of 10{1 to about 10{4 M but fails
at 10{5 M.
An Application: Carbonate Mixtures
Carbonate mixtures are particularly important because
of the central role that carbon dioxide, bicarbonate ion, and
carbonate minerals play in physiology and geochemistry.
Information about the kind and quantity of dissolved carbon-
ate species is obtained by titration. A common exercise given
to students in analytical chemistry courses is to identify the
component(s) present in solution and then calculate the
concentration of each from titration data. Interpretation of
the titration data is best related to the pH curve for carbonic
acid shown in Figure 7. The curve is easily sketched by the
method described above. It is also important to realize that
the titration curve is just as valid going from right to left as
in the conventional direction.
Figure 7 is for a natural water with pH = 6.7. The sample
is titrated with 0.002 M HCl to obtain “alkalinity” and a sec-
ond sample titrated with 0.002 M NaOH to obtain “acidity.”
Figure 5. Effect of dilution on the titration of 30.0 mL of a strong
acid (HCl) with a strong base (NaOH). The molarity is indicated
on the curves.
JChemEd.chem.wisc.edu • Vol. 76 No. 7 July 1999 • Journal of Chemical Education
In the Classroom
Conclusion
Students often learn to calculate titration curves but miss
the broader generalizations and insights that the calculations
are intended to illustrate. When doing quantitative calculations
students are confronted with a variety of special cases; for
example, strong acids and bases, weak acids and bases, before
the equivalence point, beyond the equivalence point, mono-
protic, diprotic, and what approximations might be valid. All
these cases are accompanied by the problem of solving the
resulting algebraic equations.
This is not to suggest that quantitative calculations be
neglected in teaching acid–base chemistry. Rather, it is sug-
gested that the qualitative approach described here helps to
bring the entire topic together into a cohesive overview. Once
the qualitative approach is understood students can readily
answer such questions as Given the pKa values of an acid, is
it feasible to titrate it with strong base? Is the compound
monoprotic, diprotic, etc.? What is the equivalent weight? Is
it possible to titrate a given salt as an acid? As a base?
Notes
1. The equivalent weight of phosphoric acid is seldom, if ever,
one-third of the formula weight. If titration is stopped at the first
equivalence point, then the equivalent weight is equal to the molecular
weight because only one mole of titrant is required per mole of phos-
phoric acid. If the titration is carried to the second equivalence point,
then two moles of titrant are titrated and the equivalent weight of
H3PO4 is one-half of its molecular weight. As seen in Figure 2, there is
no discernible step in pH after addition of 45 mL of titrant (the third
equivalence point). Consequently, in a titration, the equivalent weight
of phosphoric acid will never be one-third of the formula weight.
2. Some textbooks, mainly in biochemistry, have published acid–base
titration curves for amino acids that, while correct in the midrange,
show all titrations beginning abruptly at pH 1.0 and ending abruptly
at pH 14.0. Perhaps the system presented here will lead to a correction.
Mathews, C. K.; Van Holde, K. E. Biochemistry, 2nd ed.;
Benjamin/Cummings: Menlo Park, CA, 1996; p 44.
Zubay, G.; Parson, W. W.; Vance, D.E. Principles of Biochem-
istry; Wm. C. Brown: Dubuque, IA, 1994; pp 53–54.
Garrett, R. H.; Grisham, C. M. Biochemistry, 1st ed.;
Harcourt Brace Jovanovich: Orlando, FL, 1997; p 48.
Lehninger, A. L.; Nelson, D. L.; Cox, M. M. Principles of
Figure 6. Effect of dilution on the titration of 30.0 mL of a weak
acid (acetic) with a strong base (NaOH). The molarity is indicated
on the curves.
941
 In the Classroom

Figure 7. Titration curve of bicarbonate in a natural water show-

ing the definition of alkalinity and acidity. Acid titrant is 0.002 M
HCl; basic titrant is 0.002 M NaOH.

Biochemistry, 2nd ed.; Worth: New York, 1993; p 119.

3. Most anions are weak bases. The only common anions that
are too weak to be considered bases in water are the conjugate bases of
strong acids, namely, Cl {, Br{, I{, HSO4{, ClO 4{, and NO 3{, a rather
short list compared with the large number of possible anions.
4. Of course, one can always find pKb from the relation pKa +
pKb = pK w .

Literature Cited
1. Sturrock, P. E. J. Chem. Educ. 1968, 45, 258, 621.

942 Journal of Chemical Education • Vol. 76 No. 7 July 1999 • JChemEd.chem.wisc.edu