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A Kinetic−Equilibrium Study of a Triiodide Concentration Maximum

Formed by the Persulfate−Iodide Reaction
Arthur E. Burgess*,† and John C. Davidson‡
†
School of Contemporary Sciences, University of Abertay Dundee, Bell Street, Dundee, DD1 1HG, United Kingdom
‡
Kip McGrath Educational Centre, Highland House, St. Catherine’s Road, Perth, PH1 5YA, United Kingdom

ABSTRACT: The presence of triiodide, I3−, throughout the lifetime of a persulfate−iodide

reaction with persulfate in excess, is controlled by an opposing effect of falling iodide
concentration and rising iodine concentration. This brings triiodide to a concentration
maximum, [I3−]max, which can be studied by UV−visible spectroscopy using absorbance
measurements taken over an extended iodine clock time-scan. Equilibrium and conservation
equations can be combined so that, together with [I3−]max, a value of the constant K for the
equilibrium established between iodine, iodide, and the triiodide complex ion can be obtained.

KEYWORDS: Upper-Division Undergraduate, Analytical Chemistry, Laboratory Instruction, Physical Chemistry,

Aqueous Solution Chemistry, Equilibrium, Kinetics, Oxidation/Reduction, Reactions, UV−Vis Spectroscopy

I odide oxidation to iodine is the basis of an iodine clock

reaction with persulfate (peroxydisulfate), typically the
oxidant, and a small quantity of an iodine scavenger, usually
sodium thiosulfate, added to make a time-delay before the
colorful appearance of iodine provides a measure for the initial
reaction rate:1,2
S2O82 − + 2I− → 2SO24 − + I2

2S2O32 − + I2 → S4 O62 − + 2I−

A variation uses ascorbic acid as the iodine scavenger,3,4 which
is oxidized by 1:1 stoichiometry to dehydroascorbic acid:
C6H8O6 + I2 → C6H6O6 + 2H+ + 2I−
Generally, starch is added to visually enhance the first trace of
iodine that appears and marks the time-measure for the iodine
clock.
The study presented herein augments the kinetic determi-
nation of the clock reaction and follows the continuing
development of iodine in the persulfate−iodide solution, so
no starch is added. The major complex of dissolved iodine in
iodide solution is triiodide, I 3− , formed through the
equilibrium:5
I2 + I− ⇌ I−
3
The deepening yellow color of triiodide, I3−, is measured by
UV−visible absorbance spectroscopy. The increase of triiodide
concentration is shown by the steeply rising part of the
absorbance curve (Figure 1), which starts just beyond point a,
that indicates the close approaching time-measure for the clock
© 2012 American Chemical Society and
Division of Chemical Education, Inc.
Figure 1. Time-scan at λ = 352 nm with [S2O82−]0 = 50 mM, [I−]0 =
500 μM, and [ascorbic acid]0 = 50 μM near 20 °C.
reaction. Later, with persulfate in excess, the growth of triiodide
absorbance lessens appreciably, comes to a maximum, Amax, at
point b, then goes into decline. A study of this maximum
provides insight about the relationship between the iodine and
iodide concentrations at the triiodide maximum [I3−]max that
provides a method of evaluating the equilibrium constant K.
■ UV−VISIBLE ABSORBANCE TIME-SCAN
A typical reaction time-scan, similar to an initial-rate study but
extending over a longer period with persulfate in excess, was
started by quickly mixing equal volumes, kept at 20 ± 0.5 °C, of
Published: March 15, 2012
814 dx.doi.org/10.1021/ed200055t | J. Chem. Educ. 2012, 89, 814−816
Journal of Chemical Education Communication

potassium persulfate (100 mM) and a solution containing equations with respect to t. Differentiating the equilibrium
potassium iodide (1000 μM) and ascorbic acid (100 μM). A equation, (eq 1) gives
portion of the mixture was transferred into a 1 cm quartz cell at −
1 d[I3 ] d([I2][I−]) d[I ] d[I−]
the same temperature. The cell was tapped to dislodge any air = = [I−] 2 + [I2]
bubbles and then placed in the sample beam of a Shimadzu K dt dt dt dt
1650 UV−visible spectrophotometer. The wavelength λ was set When [I3−] = [I3−]max, the triiodide concentration maximum,
at 352 nm (see Figure 2), which is where triiodide strongly d[I3−]/dt = 0, and
d[I2] d[I−]
[I−] = −[I2]
dt dt (3)
Differentiating the conservation equation (eq 2), and noting
[I−]0 is constant, gives
d[I−]0 d[I−] d[I ] d[I−]
=0= +2 2 +3 3
dt dt dt dt
So, at the triiodide maximum when the rate of triiodide
formation is zero, (d[I3−]/dt = 0), the rate of iodine formation
equals half the rate of iodide removal:
d[I2] 1 d[I−]
=−
dt 2 dt (4)
Combining eq 4 with eq 3 gives the relationship between iodine
Figure 2. Color development (inset) during a persulfate oxidation of and iodide at [I3−]max:
iodide and the accompanying absorbance spectrum. [I−] = 2[I2] (5)
absorbs (molar absorptivity ε = 2.76 × 104 L mol−1 cm−1), Using the Beer−Lambert law for I3− absorbance at 352 nm,
iodine only weakly (ε = 189 L mol−1 cm−1), and iodide not at A max = εl[I−
3 ]max (6)
all,5−7 as is the case with persulfate. This spectrophotometer
had no ancillary temperature controller for the cell-holder, but where, at a wavelength of 352 nm, molar absorptivity for is ε I3−
= 2.76 × 104 L mol−1 cm−15−7 and cell length is l = 1 cm,
the surplus mixed solution was measured and remained close to
[I3−]max is obtained. The corresponding values for [I−] and [I2]
20 °C throughout the scanning period. are calculated from eqs 2 and 5 (Table 1). These values are

■ EQUILIBRIUM CONSTANT FROM ABSORBANCE

A time-scan (Figure 1) shows light absorbance by triiodide in a
Table 1. Amax and Corresponding [I3−]max, [I−], and [I2]
Using Different [I−]0 for the Persulfate−Iodide Reaction
persulfate−iodide reaction under a restricted concentration of [I−]0a/μM Amax [I3−]max/μM [I−]/μM [I2]/μM
iodide by choosing the oxidant to be in excess. This condition 1000 1.520 55 418 209
brings about the formation of iodine while iodide is being 800 1.038 38 344 172
depleted to the extent that at some point the rising 700 0.774 28 308 154
concentration of triiodide, which is dependent on both iodine 600 0.632 23 266 133
and iodide concentrations, goes into decline and a maximum 500 0.454 16 225 113
concentration of triiodide is reached. Consideration of this 400 0.305 11 184 92
maximum allows the equilibrium constant K to be determined,
a
[K2S2O8]0 = 50 mM and the reaction temperature is at 20 °C.
as follows.
then adjusted for the absorbance of I2, which, although of
Two relationships pertaining to the triiodide concentration
appreciably lower molar absorptivity at 352 nm (ε = 189 L
maximum must apply during the reaction time: mol−1 cm−15−7) than I3−, have reached proportionately much
• The formation of triiodide from iodine and iodide, which higher concentrations at Amax (Table 2).
sharply marks the conclusion of the iodine scavenger Analysis of the adjusted values using eq 1 gives a mean for K
reaction, is sufficiently rapid8 to keep [I3−] ∝ [I2][I−]. of 600 L mol−1 with a standard deviation of the sample of 24 L
This relationship with the equilibrium constant K gives mol−1; K = 600 ± 24 L mol−1 near 20 °C. This compares to Keq
the equilibrium equation = 500 using thermodynamic data obtained from visible
spectroscopy by Schmidt and Heiman.5 They determined
[I− −
3 ] = K[I2][I ] (1) ΔHO̵ = −34.2 ± 5.1 kJ mol−1 and ΔSO̵ = −65 ± 16.4 J K−1
• The sum of iodine atom concentrations throughout the mol−1 over the temperature range 296.2−332.2 K. The
reaction is equal to the initial iodide concentration, [I−]0. thermodynamic Keq at 293 K, though slightly outside of their
The mass-balance or conservation equation is temperature range, is calculated by
[I−]0 = [I−] + 2[I2] + 3[I−
3] (2) ΔGO̵ = ΔH O̵ − T ΔSO̵ = −RT ln K eq
Information about the changes with time, t, that affect each
component concentration is obtained by differentiating these Note that Keq increases in value as temperature decreases.
815 dx.doi.org/10.1021/ed200055t | J. Chem. Educ. 2012, 89, 814−816
Journal of Chemical Education Communication

Table 2. Amax Corrected for the Absorbance of I2 and the triiodide to be determined and compared to other reported
Adjusted [I3−]max, [I−], and [I2] for the Persulfate−Iodide values.
Reaction Different concentration conditions can be chosen for the
persulfate−iodide reaction and measurements made of Amax
[I−]0a/μM Amax − AI2b [I3−]max/μM [I−]/μM [I2]/μM over a range of constant temperatures. Also, similar reactions
1000 1.481 54 420 210 that generate I3− may be made for a kinetic−equilibrium study
800 1.006 36 346 173 using this absorbance maximum method; a table of iodide
700 0.745 27 310 155 oxidants can be found in ref 12.
600
500
400
0.607
0.433
0.288
22
16
10
267
226
185
134
113
93
■ AUTHOR INFORMATION
Corresponding Author
a
[K2S2O8]0 = 50 mM and the reaction temperature is at 20 °C. bThe *E-mail: setaeb@abertay.ac.uk.

absorbance of I2, ε = 189 L mol−1 cm−1, is measured at 352 nm.
Klassen, Marchington, and McGowan9 determined K at 24
°C to be 600 ± 30 L mol−1 and they cite eight other reports
that put K in the range of 650−760 L mol−1 (presumably at 25
°C) for low concentrations of I2 with no added salts. It is
■
ACKNOWLEDGMENTS
Evelyn McPhee is thanked for her able technical support,
Maurice Lindsay for his photograph of the I3− color formed in a
persulfate−iodide solution and John D. Burgess for his
assistance with the figures.

evident that determinations of K vary widely and that ionic
strength is important in this reaction involving ionic species.
Consequently, the value obtained by measuring the concen-
tration components from Amax at moderate ionic strength (due
mainly to the oxidant) is acceptable. The simplicity of this
approach augments clock reaction experiments and provides a
basis for a more extensive study of K under different
concentration conditions that includes ionic strength. Also,
given the availability of a spectrophotometer incorporating a
temperature-controlled cell holder, measuring the enthalpy
change of triiodide formation over a limited temperature range
is possible.
Contrary to a view that a large K value indicates an
equilibrium position favoring triiodide as the major form of
iodine,5 the results show that, even at [I3−]max, this is not
necessarily the case when the participants are at low
concentrations.
■
REFERENCES
(1) Moews, P. C.; Petrucci, R. H. J. Chem. Educ. 1964, 41, 549−551.
(2) Carpenter, Y-y.; Phillips, H. A.; Jakubinek, M. B. J. Chem. Educ.
2010, 87, 945−947.
(3) Wright, S. W. J. Chem. Educ. 2002, 79, 40A.
(4) Vitz, E. J. Chem. Educ. 2007, 84, 1156.
(5) Schmidt, E.; Heiman, P. J. Phys. Chem. Lab. 2005, 9, 37−41.
(6) Mamane, H.; Ducoste, J. J.; Linden, K. G. Appl. Opt. 2006, 45,
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Lykke, K. R. Photochem. Photobiol. 2003, 78, 146−152.
(8) Turner, Flynn, Sutin, and Beitz investigated the kinetics of the
triiodide equilibrium by a laser temperature-jump method and
obtained formation and reverse rate constants of (6.2 ± 0.8) × 109
L mol−1 s−1 and (8.5 ±1.0) × 106 s−1, respectively, at 25 °C. Turner,
D. H.; Flynn, G. W.; Sutin., N.; Beitz, J. V. J. Am. Chem. Soc. 1972, 94,
1554−1559.

■ IODINE CLOCK REACTION WITH A PHOTOMETRIC

END POINT
(9) Klassen, N. V.; Marchington, D.; McGowan, H. C. E. Anal. Chem.
1994, 66, 2921−2925.
(10) Skoog, D. A; Leary, J. J. Principles of Instrumental Analysis, 4th
ed.; Saunders College Publishing: Fort Worth. TX, 1992; Chap. 8, pp
The feasibility of marking the removal of the iodine scavenger 167−168 .
by a sharply defined photometric end point (point a in Figure (11) Potassium Persulfate ICSC Data. http://www.inchem.org/
1) and continuing the absorbance measurements to locate Amax documents/icsc/icsc/eics1133.htm (accessed Jan 2012).
(point b in Figure 1) has been illustrated. The aim was to (12) Harris, D. C. Quantitative Chemical Analysis, 3rd ed.; Freeman:
extend the conditions suitable for iodine clock kinetics to an New York, 1991; Chap. 16, p 415.
equilibrium study. Freshly prepared solutions of ascorbic acid
and sodium thiosulfate were both convenient delaying agents
for a well-defined photometric end point;10 however, the
presence of a time-delaying iodine scavenger was unnecessary
to take peak maximum measurements and could be excluded.
Iodide oxidation by persulfate provides a suitable basis to
make a kinetic−equilibrium study. Nevertheless, persulfate salts
are powerful oxidants and appropriate precautions are
necessary.11 Persulfate solutions also degrade over time and
fresh preparation of both this reagent and of iodide is
recommended.

■ CONCLUSIONS
The strong UV−visible absorbance of triiodide offers
opportunities to observe and measure an unusual change that
occurs to an equilibrium participant during a chemical reaction
and augments familiar iodine clock kinetic experiments and
calculations using persulfate oxidation of iodide. Measuring
Amax allows a value of the constant K for the formation of
816 dx.doi.org/10.1021/ed200055t | J. Chem. Educ. 2012, 89, 814−816