In the Laboratory
A Unified Kinetics and Equilibrium Experiment:
Rate Law, Activation Energy, and Equilibrium
Constant for the Dissociation of Ferroin
Simeen Sattar
Physics Program, Bard College, Annandale-on-Hudson, New York 12504, United States
sattar@bard.edu
Kinetics is an important topic in the general chemistry
curriculum, challenging for students regardless of their past
experience. The difficulty of this topic stems from the range
and number of concepts, encompassing determination of the rate
law by different methods, activation energy, and the relationship
between the rate law and reaction mechanism. Innumerable well-
tested experiments are available to illustrate all facets of these
topics. Equilibrium customarily follows kinetics and is often
introduced in terms of reversible kinetics. Establishing the form
of the equilibrium constant expression and studying the effects of
perturbations on the equilibrium are typical experiments.
After many years of using one experiment for the deter-
mination of a rate law, a second experiment for the determina-
tion of an activation energy, and a third experiment for the
determination of an equilibrium constant, it was felt that the
variety of chemical systems distracted students from under-
standing the underlying concepts. An experiment that com-
bines the different topics in kinetics and equilibrium by
focusing on a single chemical system was developed. The reac-
tion is a classic example from analytical and coordination
chemistry, the dissociation of tris(1,10-phenanthroline)iron-
(II), or ferroin, in acid solution:
FeðphenÞ3 2þ ðaqÞ þ 3H3 Oþ ðaqÞ /
Fe2þ ðaqÞ þ 3phenHþ ðaqÞ þ 3H2 OðlÞ
Experimental Overview
In the first week, students establish the rate law for the
reaction with respect to both ferroin and acid. In the second
week, they determine the activation energy for the reaction. In
the third and fourth weeks, they determine the equilibrium
constant. In the fifth week, students determine the base dissocia-
tion constant for phenanthroline, linking the core experiments
to acid-base equilibria, the most common application of equi-
librium in general chemistry.
The equilibrium constant and rate laws for the dissociation
and formation reactions for eq 1 were first reported by Lee,
Kolthoff, and Leussing in 1948 (1, 2). They found that the
dissociation reaction is first-order in Fe(phen)32þ and zero-order
in acid for sulfuric acid concentrations in the range 0.005-0.5 M
and Kc = (1.7 ( 0.7)  10-6 at 25 °C.1 These authors also
determined the acid dissociation constant of phenHþ. The reac-
tion rate increases dramatically with temperature, as the acti-
vation energy is relatively high. Values from 125 kJ/mol (σ =
2 kJ) (3) to 134 ( 2 kJ/mol (4) have been reported.
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r 2011 American Chemical Society and Division of Chemical Education, Inc. pubs.acs.org/jchemeduc Vol. 88 No. 4 April 2011
10.1021/ed100797s Published on Web 01/20/2011
Kinetics experiments at the general chemistry level invol-
ving this system have been described in this Journal and in at least
one commercially published laboratory manual (5-7). In all
these cases, the reaction is conducted in excess acid concentra-
tion, and in two cases at least, the reaction is presented to
students as following first-order kinetics (5, 7). Although we have
made many small changes to increase decision-making by stu-
dents, our principal innovation in the kinetics portion of the
experiment is to have students also determine the reaction order
with respect to acid concentration in the first week of the
experiment. Our second innovation is to follow the kinetics
study with a determination of the equilibrium constant for the
same system. Our third innovation is to use phenanthroline to
illustrate the determination of a pKb via pH titration. Although
not integral to the suite of experiments, it works well in terms of
timing, because the topic of weak acids and bases follows closely
on the heels of the general introduction to chemical equilibrium.
Kinetics: Rate Law and Activation Energy
For the kinetics experiment, students first run the reaction
using the concentrations chosen by Nitz et al. (7): [Fe(phen)32þ]0 =
7.5  10-5 M and [H2SO4]0 = 0.50 M. Next, the reaction is run
with the same initial ferroin concentration but 1/10 the initial
sulfuric acid concentration.2 These two experiments are con-
ð1Þ ducted in a thermostatted bath at 40 °C allowing ample time to
follow the reaction for about two half-lives within a 2.5 h lab-
oratory period. Inspection of their numerical data reveals to
students the two main features of the kinetics. First, the half-life
of the reaction is approximately constant in any given run;
second, the half-life does not change much even when the acid
concentration is reduced by a factor of 10. Although students are
prepared from classroom discussion to interpret the constancy of
the half-life in a single run as indicative of first-order kinetics, the
constancy of the half-life despite the change in acid concentra-
tion is unexpected and puzzling. A laboratory discussion can
guide students to reason that concentration independence cor-
responds to zero-order kinetics. Some students choose to make
the plots of absorbance, logarithm of the absorbance, and recip-
rocal absorbance versus time during the laboratory period (Figure 1).
The linearity of the second plot compared to the nonlinearity
of the first and third is evident. The similarity of the calculated
slopes of the first-order plots at the two different acid concen-
trations gives students another way to understand zero-order
dependence; compare the two data sets in Figure 1B. Thus,
the instructive value of this experiment is enhanced by not
revealing at the outset that reaction 1 is first-order with
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Journal of Chemical Education 457
 In the Laboratory
Figure 1. Filled circles show the zero- (A), first- (B), and second-order (C)
plots for [Fe(phen)32þ]0 = 7.5  10-5 M and [H2SO4]0 = 0.50 M at
40 °C; open circles in (B) are for [H2SO4]0 = 0.05 M. In (B), k = (1.2 (
0.1)  10-3 s-1 (continuous line, 0.5 M H2SO4) and k = (1.1 ( 0.3) 
10-3 s-1 (dashed line, 0.05 M H2SO4). Student data are shown.
respect to Fe(phen)32þ and not ignoring the acid indepen-
dence of the reaction.
From the moment rate laws are introduced, students are
impatient to understand their significance. Consequently, they
are deeply satisfied to discover the connection between the observed
rate law and reaction mechanism. The reason for the emphasis
on determining rate laws and why they cannot be deduced from
the coefficients in the balanced reaction are clear at last. In the
present reaction, eq 1, the discrepancy between the rate law
Rate ¼ k½FeðphenÞ3 2þ 
and stoichiometric coefficients can be profitably discussed in
class. The discrepancy immediately indicates that the reaction
cannot occur in one step. Students can be led to develop a
mechanism starting with the rate-determining step:
FeðphenÞ3 2þ ðaqÞ f FeðphenÞ2 2þ ðaqÞ þ phenðaqÞ ð2Þ
With this first step, the remainder of the mechanism falls into
place for students. Students readily conjecture that the steps
needed to give the overall reaction are stepwise dissociation of
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458 Journal of Chemical Education Vol. 88 No. 4 April 2011
Figure 2. Arrhenius plot of student data and best-fit line for the dissocia-
tion of ferroin. Four sets of data are included to show the typical variation.
An unweighted linear least-squares fit of all the data gives Ea = 127 (
15 kJ/mol.
Fe(phen)22þ and protonation of phenanthroline and that these
steps must be rapid by comparison with reaction 2 (2, 6).
Among the smaller changes we made to the published pro-
cedures are that the class collectively records a spectrum of
Fe(phen)32þ and determines the appropriate wavelength for
monitoring the reaction (510-512 nm). A recommendation
is made to sample the reaction solution (in the 40 °C bath) at
3 min intervals to start with and adjust the time as the reaction
proceeds. Students are surprisingly reluctant to deviate from
strict regularity, but eventually admit the sense of lengthening the
time intervals. This experience illuminates what it means for a
reaction to slow down with time more effectively than classroom
discussion and graphs. In the second week of the kinetics exper-
iment, when students run the reaction in baths at 30, 50, and
60 °C, they are asked to rely on the previous week's experience
and their understanding of the effect of temperature on reaction
rates to choose appropriate time intervals. The reaction is fast
enough at 50 and 60 °C for students to repeat the runs in case
their initial choices of time intervals are too long.
As the temperature is raised from 30 to 60 °C, the half-life
of the reaction decreases precipitously from about 90 to 1 min.
An Arrhenius plot typical of those obtained by students is shown
in Figure 2. Activation energies obtained by students are in good
agreement with literature values.
Dissociation Constant for Ferroin
The equilibrium constant for reaction 3, the reverse of reaction
1, is determined in the third and fourth weeks of the experiment:
Fe2þ ðaqÞ þ 3phenHþ ðaqÞ þ 3H2 OðlÞ /
FeðphenÞ3 2þ ðaqÞ þ 3H3 Oþ ðaqÞ ð3Þ
Our experimental design is similar to that for the popular iron-
(III)-thiocyanate equilibrium constant determination (8-10).
Students prepare solutions with known initial millimolar con-
centrations of the reactants in 0.50 M H2SO4. Consequently, the
hydrogen ion concentration is essentially fixed. The equilibrium
ferroin concentration is determined spectrophotometrically and
used to calculate the equilibrium concentrations of the reactants.
Reactant concentrations close to those used in the 1948 study are
employed (1). Sulfuric acid is treated as a strong monoprotic acid,
as it was for the first kinetics experiment.
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pubs.acs.org/jchemeduc r 2011 American Chemical Society and Division of Chemical Education, Inc.

Figure 3. Titration curve for 20 mL of 0.01 M phenanthroline titrated
with 0.022 M HCl (filled circles, left axis). Slope of the titration curve,
|ΔpH|/Δvolume HCl (open circles, right axis). The peak maximum
corresponds to a pKb of 9.3. Dashed curves serve to guide the eye.
In the first week of this experiment, students prepare the
“equilibrium” solutions by diluting stock solutions of FeSO4 and
phenanthroline with 0.50 M H2SO4. They also prepare standard
solutions for making the calibration curve. Students must decide
how to make all required solutions. As the reaction is slow to
equilibrate at room temperature, absorbance measurements are
recorded in the second week.
In the second week, students record the absorbances of the
equilibrium and standard solutions. They also observe the effect
of temperature on equilibrium by immersing one of their equil-
ibrated solutions in a warm water bath. Interpretation of the
fading of the red color vis-
a-vis the sign of ΔrH provokes a
surprising amount of debate among students, even though Le
Ch^atelier's principle has been previously discussed in the class-
room with accompanying demonstrations.
A Beer's law plot is constructed from class data during the
laboratory period. Students complete at least one calculation of
the equilibrium constant during the laboratory period and are
encouraged to use a spreadsheet (a template is not provided)
rather than a calculator. For many students, this is the most
elaborate spreadsheet calculation they have done, so the time is
well spent. In the next few days, students submit their calculated
equilibrium constants to the instructor for verification. A spread-
sheet containing all the calculated values is then made available to
all students. (Students transform the equilibrium constants for
the formation reaction 3 to that for the dissociation reaction,
eq 1). The larger pool of results permits students to assess the
accuracy and precision of class results for Kc. Order-of-magni-
tude agreement with the literature value with a similar relative
uncertainty is obtained, for example, Kc = (2.7 ( 0.8)  10-6.
Base Dissociation Constant for Phenanthroline
Determination of dissociation constants for weak acids and
bases by pH titration is a common experiment accompanying the
topic of weak acids and bases in the classroom. For the fourth and
final experiment in this suite, students are given the problem of
determining the pKb for phenanthroline (along with the pKa for
a weak acid). Students are expected to devise their own procedure
(titration curves have been discussed in the classroom by this
time). Phenanthroline is a good choice to contrast with acetic or
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r 2011 American Chemical Society and Division of Chemical Education, Inc.
In the Laboratory
formic acid. As a very weak base (pKb = 9.14) with low solubility
in water, the phenanthroline titration curve poses more of an
experimental and interpretive challenge. A typical student titra-
tion curve is shown in Figure 3. Students use a simple two-point
finite difference formula to locate the inflection point in the
titration curve and obtain good agreement with the literature
values. Some students continue the titration beyond the expected
second equivalence point and are surprised by its absence. This
can become an additional topic of discussion in the laboratory or
during class.
Hazards
Iron(II) sulfate, ferroin, and 1,10-phenanthroline may irri-
tate the eye and skin. In addition, as 1,10-phenanthroline is toxic
to aquatic life, it should not be released into the environment.
Sulfuric acid and hydrochloric acid are corrosive and can be
dangerous to the eyes and skin; safety goggles must be worn.
Summary
The dissociation of tris(1,10-phenthroline)iron(II) in acid
solution has proven to be a versatile system for general chemistry
students to investigate. We have extended a published experi-
ment in which students determined the rate law with respect to
only the complex ion and activation energy to include determi-
nation of the order with respect to acid and the equilibrium
constant. The simplicity of the rate law is an attractive feature of
this reaction for instructors who choose to introduce reaction
mechanisms into their course. In the final experiment, the base
dissociation constant of the ligand is determined; this serves as a
natural bridge to the topic of acids and base equilibria that fol-
lows the general introduction to chemical equilibrium.
Acknowledgment
I thank my students in Basic Principles of Chemistry II in
2008 and 2009 for the use of their data and Robert Olsen for a
critical reading of the manuscript. I am grateful to the reviewers
for their valuable suggestions.
Notes
1. This is the “concentration equilibrium constant” not the “activity
equilibrium constant” whose value is (4 ( 2)  10-7 (1).
2. Students are instructed to assume H2SO4 is a strong mono-
protic acid at both 0.50 and 0.05 M. This assumption is
examined when the topic of polyprotic acids arises in class. It
is found to be correct for the 0.50 M solution, but the
nominally 0.05 M solution is closer to 0.06 M in [Hþ].
Literature Cited
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70, 2348.
2. Lee, T. S.; Kolthoff, I. M.; Leussing, D. L. J. Am. Chem. Soc. 1948,
70, 3596.
3. Burgess, J.; Prince, R. H. J. Chem. Soc. 1963, 5752.
4. Basolo, F.; Hayes, J. C.; Neumann, H. M. J. Am. Chem. Soc. 1954,
76, 3807.
5. Twigg, M. V. J. Chem. Educ. 1972, 49, 371.
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In the Laboratory
6. Edwards, J. O.; Edwards, K.; Palma, J. J. Chem. Educ. 1975, 52, 408.
7. Nitz, O. W.; Ondrus, M. G.; Melton, T. Laboratory Manual for
Introductory Chemistry; Wm. C. Brown: Dubuque, IA, 1993.
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in the Laboratory, 6th ed.; Saunders: Fort Worth, TX, 1996.
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460 Journal of Chemical Education Vol. 88 No. 4 April 2011
10. Nelson, J. H.; Kemp, K. C. Laboratory Experiments; Pearson
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Supporting Information Available
Instructors' notes; instructions for students. This material is
available via the Internet at http://pubs.acs.org.
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pubs.acs.org/jchemeduc r 2011 American Chemical Society and Division of Chemical Education, Inc.