In the Laboratory
Class Projects in Physical Organic Chemistry:
The Hammett Equation
Peter S. Marrs
Department of Chemistry, University of Victoria, Victoria, BC V8W 3P6, Canada; Pmarrs @uvic.ca
The Hammett equation is studied in two 3rd-year organic
chemistry courses at the University of Victoria. In Chemistry
338 (Topics in Structure and Reactivity) and Chemistry 337
(Bio-organic Chemistry), the topic is studied as a means of
understanding how structure can relate to reactivity and how
structure can affect reaction rates. The exercise presented here
provides a hands-on demonstration of the Hammett equation
in the laboratory.
The experiment is presented as a class project. A students
individual data points are collected by the course coordinator,
who shares a completed data set with the entire class. This has
the advantage that a student may study a larger data set without
increasing the time spent in the laboratory. Two students can
complete the work described in one 3-hour laboratory period
using one UV spectrometer.
Background
The linear free energy relationship known as the
Hammett equation was described by L. P. Hammett in 1937
(1). The equation was extensively reviewed by Jaffe in 1953(2)
and more recently by Hansch, Leo and Taft (3). Hammetts
equation is but one of many equations describing linear free
energy relationships; however, it is the one most often taught
to undergraduate students (4 ).
The standard reaction for the Hammett equation is the
ionization of benzoic acids in water at 25 C (Scheme I).
CO 2H CO 2-
KX
+ H+
X X
Scheme I
The Hammett equation has the form shown in eq 1:
KX
log = (1)
KH
where KH and KX are the acidity constants of benzoic acid and
the substituted benzoic acid, respectively, is the substituent
constant, dependent on the group X, and is called the reac-
tion constant. For the standard reaction, is defined as +1.
The Hammett equation relates structure and reactivity via
the substituent constant . The values represent a summation
of the electronic effects (induction and resonance) of the sub-
stituent attached to the aromatic ring. The position of a sub-
stituent relative to the reacting group on the aromatic ring
also has an effect on , and the values differ between the meta
and para positions. Substituents that are ortho to the reacting
group are not included in the Hammett equation, since ortho
groups often exhibit steric effects that mask the electronic
effects.
JChemEd.chem.wisc.edu Vol. 78 No. 4 April 2001 Journal of Chemical Education
W
Substituents that can stabilize a negative charge by either
induction or resonance have positive values, whether they are
on a meta or para position (e.g., NO2: p = 0.81, m = 0.71).
Likewise, substituents that can stabilize a positive charge
through induction or resonance have negative values for
both possible orientations. The values for meta and para are
similar, though not identical. Interesting cases arise for sub-
stituents such as methoxy (OCH3). This group is inductively
withdrawing (via the electronegative O atom) but resonance
donating (via the lone pair electrons on the O). The values
vary greatly between the two possible positions (p =
0.28,
m = +0.10).
Reactions exist where the charge formed on the reacting
group can be delocalized onto the aromatic ring and onto
the substituent. The ionization of phenols demonstrates this
delocalization. This is shown in Scheme II, using a 4-
hydroxybenzaldehyde as an example.
OH O- O
- H+
H
H H
O O O-
Scheme II
These reactions cannot be described by . The substituent
constants are modified for these reactions to account for the
ability of the substituent to delocalize the charge. For reactions
that develop a negative charge on the reacting group, p
values
are available; values of m
dont differ much from m and are
not reported separately. Values for p+ and m+ exist for reactions
that develop a positive charge on the reacting group.
The reaction constant is a measure of how sensitive a
reaction is to the electronic effects of the substituent. Values
of close to zero indicate an insensitivity to the effect of the
substituent, whereas larger values of show a greater sensi-
tivity. The sign of is also important. Positive values of
indicate that the reaction is enhanced by electron-withdrawing
substituents, and negative values of show that the reaction
is enhanced by electron-donating substituents.
Summary and Discussion of the Experiment
The ionization of substituted phenols (Scheme III) is the
reaction studied in this experiment. This is, in fact, the stan-
dard reaction for determining p
(2). In this exercise, litera-
ture values of both p and p
are provided (3), and the stu-
dents must determine (i) which substituent constant is more
appropriate for the reaction studied and (ii) the reaction con-
stant for the ionization of phenols in water.
OH O
H 2O
+ H+
X X
Scheme III
527
 In the Laboratory

In aqueous solution, the extent of the ionization can be 3.5

seen to be pH dependent. In concentrated acid, the phenol 3.0

will be completely protonated, whereas in concentrated base,
2.5
it will be completely deprotonated. In a buffered solution near

pKH pKX
the pKa of the phenol, both protonated and deprotonated 2.0

species will exist. 1.5

The equilibrium constant for the dissociation of a weak 1.0
acid (HX) is given by eq 2:
0.5
+

H X HX 0.0
K= and
log K =
log H+ + log (2)
HX
-0.5
X -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0

Since pKa =
log K and pH =
log [H+], we have the p

HendersonHasselbalch equation (eq 3). If it is possible to Figure 1. Plot of pKH pKX vs p.
determine [HX] and [X
] at a known pH, the pKa of the weak
acid, in this case the phenol, may be determined.
HX
pK a = pH + log (3) 3.5
X
3.0
The pKa of a phenol may be determined spectrophoto- 2.5
metrically. The UV spectrum of the protonated phenol is very

pKH pKX
2.0
different from the spectrum of the deprotonated phenol. At
any pH, the spectrum of the phenol solution is the sum of 1.5
the spectra of each of the protonated and deprotonated forms 1.0
of the phenol, multiplied be the mole fraction of each form
0.5
present in the solution. Thus, at any particular wavelength,
the total absorbance A of the phenol solution is given by eq 4 0.0

-0.5
A = A X
+ 1 A HX (4) -0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

where AX
and AHX are the absorbances of the deprotonated
and protonated forms of the phenol, and is the mole fraction
of the deprotonated phenol. This equation can be rearranged to
calculate the mole fraction of the deprotonated phenol (eq 5):
A A HX
= (5)
A X
A HX
The mole fractions of X
and HX can be used in eq 4 to
calculate the pKa of the phenol (eq 6):
1 In collecting the class results, the coordinator presents
pK a = pH + log (6)
Solutions of the phenols and the buffers are available for
the students, and a calibrated pH meter is used to determine
the exact pH of the buffers. Suggestions for the appropriate
buffers and a suitable wavelength range are given for each
phenol. Each student is assigned three phenols (of 10 possible)
to determine the pKa, and the students data are combined
with those of other students.
Three spectra are required to determine the pKa of a phenol:
1. The phenol in 0.1 M acid solution, where the only
species present is the protonated phenol HX.
2. The phenol in 0.1 M base solution, where the only
species present is the deprotonated phenol X
.
3. The phenol in a buffer solution, where the pH of the
buffer is close to the pKa of the phenol. Both proto-
nated and deprotonated species are present in this
solution.
p

Figure 2. Plot of pKH pKX vs p
.
Two buffer solutions are used, and the pKa calculations
are carried out at four wavelengths to ensure consistent results.
This provides eight pKa values for each phenol studied. The
students compute an average pKa for each of their phenols
and submit these values to the laboratory coordinator. The
coordinator collects the class results and makes them available
to all of the students.
all data points submitted, without identifying the student
who submitted the data. This gives multiple pKa values for
each phenol studied. The coordinator does not average the
pKa values, but obviously erroneous points are flagged. The
student must decide whether to use one of the data points
for each phenol, or if computing an average of the data points
is more appropriate. This makes the student think critically
about the collected data.
The Hammett equation may be rewritten as eq 7:
log K X log K H = (7)
and by recognizing that pKa =
log Ka, eq 7 may then be
written as eq 8:
pK H pK X = (8)
The pKa values determined by the students may be used
directly. Plots of pKH pKX vs p and pKH pKX vs p
,
made from student data, are shown in Figures 1 and 2. The

528 Journal of Chemical Education Vol. 78 No. 4 April 2001 JChemEd.chem.wisc.edu


correlation of the pKa differences with p are clearly poor (r 2 =
.702), whereas the correlation with p
is excellent (r 2 = .994).
The reaction constant is computed as the slope of the graph,
and is equal to 2.24 (lit. 2.11) (2). This demonstrates (not
surprisingly) that for the appropriate substituent, the charge
on the phenoxide may be delocalized onto the substituent.
This experiment was tried in the fall 1998 and fall 1999
classes of Chemistry 338 (45 and 33 students, respectively)
with excellent results. The laboratory reports submitted by the
students showed their ability to use the data as required. The
discussion sections of their lab reports showed an
understanding of the Hammett equation and an understand-
ing of the application of p and p
to the ionization of
phenols.
Hazards
Some of the buffer components are caustic, and many
of the phenols are toxic; however, the preparation of the
solutions is handled by a technician. Thus, for the students,
standard laboratory safety practices (safety glasses, gloves, and
laboratory coats) should suffice for this experiment.
JChemEd.chem.wisc.edu Vol. 78 No. 4 April 2001 Journal of Chemical Education
In the Laboratory
Acknowledgments
I thank the students and teaching assistants of Chemistry
338, classes of 1998 and 1999, for their input and suggestions
for this experiment.
W
Supplemental Material
Instructions for students and notes for the instructor are
available in this issue of JCE Online.
Literature Cited
1. Hammett, L. P. J. Am. Chem. Soc. 1937, 59, 96.
2. Jaffe, H. H. Chem. Rev. 1953, 53, 191.
3. Hansch, C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, 165.
4. This is illustrated by the ten papers relating to the Hammett
equation published in the Journal of Chemical Education since
1961: Leisten, J. A. 1961, 38, 302. Schreck, J. O. 1971, 48, 103.
Salmon, M.; Jimenez, A.; Salazar, I.; Zawadzki, R. 1973, 50,
370. Henri-Rousseau, O.; Texier, F. 1978, 55, 437. Blunt, J. W.;
Happer, D. A. R. 1979, 56, 56. Gortler, L. 1985, 62, 752.
Seeman, J. I. 1986, 63, 42. Hathaway, B. A.; Olesen, B. 1993, 70,
953. Schwan, A. L. 1993, 70, 1001. Setliff, F. L.; Soman, N. G.;
Toland, A. D. 1995, 72, 362.
529