Chemical Education Today
Letters
Discussion: Should Students Calculate
Titration Curves?
After working in industrial analytical laboratories for twen-
ty years, I became an academic and taught analytical chemistry.
I wondered why this should include calculating titration curves,
since I had never had occasion to do so as an analyst. I have since
taught hundreds of analytical students and thousands of intro-
ductory students to do such calculations but still see no purpose
in it for either course. The calculations do not help students to
understand titrimetry. Students concentrate their attention on
learning the algorithms but still fail to understand the basic
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.
principles. They do not understand the effect of equilibrium
at the equivalence point, nor the usefulness of logarithmic re-
lationships. It is an example of the principle asserted by Moore
Downloaded via UNIV DE ALICANTE on December 23, 2022 at 21:47:39 (UTC).
(1) that students who can answer numerical questions do not
necessarily understand their chemistry. It provides an exercise
in equilibrium calculations for which they otherwise have little
use (2, 3). Consider:
At the equivalence point the concentration of analyte must
change from small to negligible after the addition of one
increment of titrant (similarly, the concentration of titrant
must change from negligible to small). If the reaction
reverses too readily, then near the equivalence point the
reverse reaction produces a significant quantity of analyte.
Then the change in concentration of the analyte from small
to negligible takes several increments of titrant and the end
point is difficult to detect so that tricks must be used to find
the equivalence point.
One cure is to use a more powerful titrant such as
CH3CO2H2+ in acetic acid instead of H3O+ or C2H5O– in
ethanol instead of OH– . Another is to remove the reaction
product so that the reaction cannot reverse.
Another trick uses a logarithmic monitor such as a poten-
tiometric electrode with an output that is linear with the
logarithm of the concentration. In the theoretical limiting
case where the reaction actually does go to completion, the
concentration of the analyte becomes zero at the equivalence
point and its logarithm becomes minus infinity. The change
in the logarithm of the analyte concentration with one in-
crement of titrant is then infinite. In real cases, the reaction
merely approaches completion. Near the equivalence point
498 Journal of Chemical Education  •  Vol. 85  No. 4  April 2008  •  www.JCE.DivCHED.org  •  © Division of Chemical Education
where the analyte concentration is low and the concentra-
tion of reaction product is high, the reaction has some ten-
dency to reverse. Then the logarithm of the change between
a low concentration and a negligible one is not infinite but
it is substantial. The sharpest change in the logarithm is at
the equivalence point or as near to it as makes no difference
(except in special extreme cases that are not discussed in
undergraduate courses; ref 4). When the point of sharpest
change is unclear then the recourse is to plot the derivative
or the second derivative.
None of this reasoning is helped by calculating the titration
curve. Worse, calculating the curve devotes attention to unim-
portant parts of the titration.
Decades ago when titrimetry was the almost exclusive
method of quantitative analysis, it was sometimes necessary
to calculate multiple equilibria to design a titrimetric method
that avoided interferences. These were the subject of graduate
courses in analytical chemistry and did require the calculation
of titration curves. It would be very rare in the 21st century for
such calculations to be useful.
Calculation of titration curves should not be taught in un-
dergraduate analytical courses and a fortiori not in introductory
chemistry. There are more important subjects on which students
should spend their study time (5).
Literature Cited
1. Moore, J. W. J. Chem. Educ. 2004, 81, 7.
2. Hawkes, S. J. J. Chem. Educ. 2003, 80, 1381.
3. Lewis, D. L. J. Chem. Educ. 2004, 81, 1265.
4. Roller, P. S. J. Amer. Chem. Soc. 1928, 50, 1.
5. Hawkes, S. J. J. Chem. Educ. 2005, 82, 1615.
Supporting JCE Online Material
http://www.jce.divched.org/Journal/Issues/2008/Apr/abs498_1.html
Full text (HTML and PDF) with links to cited URLs and JCE articles
Stephen J. Hawkes
Department of Chemistry
Oregon State University
Corvallis, OR 97331-4003
stephen.hawkes@orst.edu