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A KineticEquilibrium Study of a Triiodide Concentration Maximum Formed by the PersulfateIodide 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. Catherines Road, Perth, PH1 5YA, United Kingdom
ABSTRACT: The presence of triiodide, I3 , throughout the lifetime of a persulfateiodide 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 UVvisible 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, UVVis Spectroscopy 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
2 S2O8 + 2I 2SO2 4 + I2
2 2 2S2O3 + I2 S4 O6 + 2I

A variation uses ascorbic acid as the iodine scavenger,3,4 which is oxidized by 1:1 stoichiometry to dehydroascorbic acid:
+ + 2I C6H8O6 + I2 C6H6O6 + 2H
2 Figure 1. Time-scan at = 352 nm with [S2O8 ]0 = 50 mM, [I]0 = 500 M, and [ascorbic acid]0 = 50 M near 20 C.

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 determination of the clock reaction and follows the continuing development of iodine in the persulfateiodide solution, so no starch is added. The major complex of dissolved iodine in iodide solution is triiodide, I 3 , formed through the 5 equilibrium:
I2 + I I 3
The deepening yellow color of triiodide, I3 , is measured by UVvisible 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.

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 ]max that iodide concentrations at the triiodide maximum [I3 provides a method of evaluating the equilibrium constant K.

UVVISIBLE 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
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dx.doi.org/10.1021/ed200055t | J. Chem. Educ. 2012, 89, 814816

Journal of Chemical Education potassium persulfate (100 mM) and a solution containing potassium iodide (1000 M) and ascorbic acid (100 M). A portion of the mixture was transferred into a 1 cm quartz cell at the same temperature. The cell was tapped to dislodge any air bubbles and then placed in the sample beam of a Shimadzu 1650 UVvisible spectrophotometer. The wavelength was set at 352 nm (see Figure 2), which is where triiodide strongly

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equations with respect to t. Differentiating the equilibrium equation, (eq 1) gives

d([I2][I]) d[I ] 1 d[I3 ] d[I] = = [I] 2 + [I2] K dt dt dt dt
When [I3 ] = [I3 ]max, the triiodide concentration maximum, d[I3 ]/dt = 0, and

[I]

d[I2] d[I] = [I2] dt dt

(3)

Differentiating the conservation equation (eq 2), and noting [I]0 is constant, gives
d[I] d[I]0 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
Figure 2. Color development (inset) during a persulfate oxidation of iodide and the accompanying absorbance spectrum. (4)

Combining eq 4 with eq 3 gives the relationship between iodine and iodide at [I3 ]max:
[I] = 2[I2]
(5)
I3

absorbs (molar absorptivity = 2.76 104 L mol1 cm1), iodine only weakly ( = 189 L mol1 cm1), and iodide not at all,57 as is the case with persulfate. This spectrophotometer had no ancillary temperature controller for the cell-holder, but the surplus mixed solution was measured and remained close to 20 C throughout the scanning period.

Using the BeerLambert law for

A max = l[I 3 ]max

absorbance at 352 nm,

(6)
I3

A time-scan (Figure 1) shows light absorbance by triiodide in a persulfateiodide reaction under a restricted concentration of iodide by choosing the oxidant to be in excess. This condition brings about the formation of iodine while iodide is being depleted to the extent that at some point the rising concentration of triiodide, which is dependent on both iodine and iodide concentrations, goes into decline and a maximum concentration of triiodide is reached. Consideration of this maximum allows the equilibrium constant K to be determined, as follows. Two relationships pertaining to the triiodide concentration maximum must apply during the reaction time: The formation of triiodide from iodine and iodide, which sharply marks the conclusion of the iodine scavenger ] [I2][I]. reaction, is sufficiently rapid8 to keep [I3 This relationship with the equilibrium constant K gives the equilibrium equation
[I 3 ] = K[I2][I ]
(1)

where, at a wavelength of 352 nm, molar absorptivity for is = 2.76 104 L mol1 cm157 and cell length is l = 1 cm, [I3 ]max is obtained. The corresponding values for [I] and [I2] are calculated from eqs 2 and 5 (Table 1). These values are
Table 1. Amax and Corresponding [I3 ]max, [I], and [I2] Using Different [I ]0 for the PersulfateIodide Reaction

EQUILIBRIUM CONSTANT FROM ABSORBANCE

[I]0a/M 1000 800 700 600 500 400

a

Amax 1.520 1.038 0.774 0.632 0.454 0.305

[I3 ]max/M

[I]/M 418 344 308 266 225 184

[I2]/M 209 172 154 133 113 92

55 38 28 23 16 11

[K2S2O8]0 = 50 mM and the reaction temperature is at 20 C.

The sum of iodine atom concentrations throughout the reaction is equal to the initial iodide concentration, [I]0. The mass-balance or conservation equation is
[I]0 = [I] + 2[I2] + 3[I 3]
(2)

then adjusted for the absorbance of I2, which, although of appreciably lower molar absorptivity at 352 nm ( = 189 L , have reached proportionately much mol1 cm157) than I3 higher concentrations at Amax (Table 2). Analysis of the adjusted values using eq 1 gives a mean for K of 600 L mol1 with a standard deviation of the sample of 24 L mol1; K = 600 24 L mol1 near 20 C. This compares to Keq = 500 using thermodynamic data obtained from visible spectroscopy by Schmidt and Heiman.5 They determined HO = 34.2 5.1 kJ mol1 and SO = 65 16.4 J K1 mol1 over the temperature range 296.2332.2 K. The thermodynamic Keq at 293 K, though slightly outside of their temperature range, is calculated by
GO = H O T SO = RT ln K eq

Information about the changes with time, t, that affect each component concentration is obtained by differentiating these
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Note that Keq increases in value as temperature decreases.

dx.doi.org/10.1021/ed200055t | J. Chem. Educ. 2012, 89, 814816

Journal of Chemical Education Table 2. Amax Corrected for the Absorbance of I2 and the Adjusted [I3 ]max, [I], and [I2] for the PersulfateIodide Reaction
[I]0a/M 1000 800 700 600 500 400 Amax AI2b 1.481 1.006 0.745 0.607 0.433 0.288
[I3 ]max/M

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[I]/M 420 346 310 267 226 185

[I2]/M 210 173 155 134 113 93

54 36 27 22 16 10

triiodide to be determined and compared to other reported values. Different concentration conditions can be chosen for the persulfateiodide reaction and measurements made of Amax over a range of constant temperatures. Also, similar reactions that generate I3 may be made for a kineticequilibrium study using this absorbance maximum method; a table of iodide oxidants can be found in ref 12.

AUTHOR INFORMATION

a [K2S2O8]0 = 50 mM and the reaction temperature is at 20 C. bThe absorbance of I2, = 189 L mol1 cm1, is measured at 352 nm.

Corresponding Author

*E-mail: setaeb@abertay.ac.uk.

Klassen, Marchington, and McGowan9 determined K at 24 C to be 600 30 L mol1 and they cite eight other reports that put K in the range of 650760 L mol1 (presumably at 25 C) for low concentrations of I2 with no added salts. It is 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 concentration 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.

ACKNOWLEDGMENTS Evelyn McPhee is thanked for her able technical support, color formed in a Maurice Lindsay for his photograph of the I3 persulfateiodide solution and John D. Burgess for his assistance with the figures. REFERENCES
(1) Moews, P. C.; Petrucci, R. H. J. Chem. Educ. 1964, 41, 549551. (2) Carpenter, Y-y.; Phillips, H. A.; Jakubinek, M. B. J. Chem. Educ. 2010, 87, 945947. (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, 3741. (6) Mamane, H.; Ducoste, J. J.; Linden, K. G. Appl. Opt. 2006, 45, 18441856. (7) Rahn, R. O.; Stefan, M. I.; Bolton, J. R.; Goren, E.; Shaw, P.-S.; Lykke, K. R. Photochem. Photobiol. 2003, 78, 146152. (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 mol1 s1 and (8.5 1.0) 106 s1, respectively, at 25 C. Turner, D. H.; Flynn, G. W.; Sutin., N.; Beitz, J. V. J. Am. Chem. Soc. 1972, 94, 15541559. (9) Klassen, N. V.; Marchington, D.; McGowan, H. C. E. Anal. Chem. 1994, 66, 29212925. (10) Skoog, D. A; Leary, J. J. Principles of Instrumental Analysis, 4th ed.; Saunders College Publishing: Fort Worth. TX, 1992; Chap. 8, pp 167168 . (11) Potassium Persulfate ICSC Data. http://www.inchem.org/ documents/icsc/icsc/eics1133.htm (accessed Jan 2012). (12) Harris, D. C. Quantitative Chemical Analysis, 3rd ed.; Freeman: New York, 1991; Chap. 16, p 415.

IODINE CLOCK REACTION WITH A PHOTOMETRIC END POINT The feasibility of marking the removal of the iodine scavenger by a sharply defined photometric end point (point a in Figure 1) and continuing the absorbance measurements to locate Amax (point b in Figure 1) has been illustrated. The aim was to extend the conditions suitable for iodine clock kinetics to an 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 kineticequilibrium 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
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dx.doi.org/10.1021/ed200055t | J. Chem. Educ. 2012, 89, 814816