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CHEM 423 Physical Chemistry Laboratory

Supplemental Procedure: Chemical Equilibrium in Solution
Introduction
The theoretical background for this experiment is given in Experiment 12 of the Garland, et
al. text. Our goal is to measure the equilibrium constant for the room temperature aqueous
reaction
I2 (aq) + I (aq) I3 (aq)

(1)

(You will want to measure and report room temperature on the day of your experiment.)
Following the discussion in the text (see Eq. 2 of Experiment 12 in the text), the equilibrium
constant (in concentration units) is given by
Kc =

[I3 ]
[I2 ][I ]

(2)

The procedure in the text relies on titrations to determine the concentration of I2 by redox
reaction with thiosulfate and also measuring a heterogeneous partitioning of I2 between an
aqueous phase and an organic phase. The titrations are tedious, and the organic solvents in
which I2 is soluble are toxic and/or highly volatile.
A more direct procedure is to measure the concentration of the triiodide ion product by
absorption spectrophotometry, and to deduce the concentrations of I2 and I from the stoichiometry of the reaction in Eq. 1. That is the method we will use here.
Experimental approach
Imagine we add the reactants I2 and I to water solvent such that their initial concentrations
are known to be
[I2 ] = a
[I ] = b

(3)
.

(4)

The following table tracks the change in these initial concentrations as equilibrium is established:
initial
change
final

[I2 ]
a
x
ax

[I ]
b
x
bx

[I3 ]
0
+x
x

Substitution of the final, equilibrium concentrations into Eq. 2 gives

Kc =

x
(a x)(b x)

(5)

Recall that we will be measuring spectroscopically the equilibrium concentration of the triiodide, x. Let us manipulate Eq. 5 to obtain Kc from a measurement of x as a function of the
known initial concentrations a and b.

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We begin by rearranging Eq. 5:
x = Kc (a x)(b x)

(6)

We make the definitions

y
z

x
a
b
a

(7)
.

(8)

We see that z is the ratio of the initial concentrations of the reactants and the y is the ratio of
the final concentration of the triiodide product to the initial concentration of the I2 . Dividing
Eq. 6 by a2 and rewriting in terms of y and z gives
x
a2
x/a2
1 x/a
y
a(1 y)



x b x

= Kc 1
a
a a


b x
= Kc

a a


= Kc (z y)

(9)
(10)
(11)

A plot of the left side of Eq. 11 versus z y should give a straight line with slope Kc .
Experimental procedure
1. Solutions
(a) KI solution.
Prepare (starting with a TA-provided stock solution, if available) a 0.100 M solution
of KI(aq). Again, it is not critical that this solution be exactly 0.100 M, but its actual
concentration must be accurately known.
(b) I2 solutions.
Your TA will provide a TA stock solution of I2 (aq) at a known concentration
(appoximately 0.4 mM). Please use special care to not contaminate this TA stock
solution. Because I2 has a high vapor pressure, it is important to keep the TA stock
solution flask capped when not in use.
Starting with this stock solution, prepare your own solutions of I2 (aq) in small volumetric flasks (e.g. 10 mL) at concentrations of approximately 0.030 and 0.060 mM.
These exact concentrations are not important, but it is important that you know
the accurate concentrations of your two I2 solutions.
(c) I2 /KI solutions.
Finally, prepare two solutions with the same concentrations of I2 as prepared in
Sec. 1b above, but with a large excess of KI. This can be accomplished by using the
KI solution prepared in Sec. 1a to dilute the TA I2 stock solution. The large excess
of KI will (by Le Chateliers principle) convert all the I2 into I
3.

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2. Absorption measurements
Using a volumetric pipette, deliver 3.00 mL of one of your I2 solutions into a fused
silica cuvette. Record its absorption spectrum between 300-650 nm on the Agilent/HP
8453 Diode Array Absorption Spectrophotometer. This initial spectrum will become
the background spectrum for this particular I2 concentration, and will be subtracted
from the spectra recorded as KI is added. This background spectrum will show a broad
absorption feature near 400 nm corresponding to I2 (aq), with very little absorption at

353 nm, where I

3 (aq) is known to absorb. [The molar absorptivity of I3 at 353 nm is
26,400 L/mol cm and that of I2 is 18 L/mol cm. (Awtrey, A. D.; Connick, R. E. J.
Am. Chem. Soc. 1951, 73, 1842.)]
Next use a syringe to add successive aliquots of 2 L of the KI solution (prepared in
Sec. 1a) to the cuvette, measuring the absorption spectrum after each addition up to a
total addition of 20 L. Shake the cuvette after each addition to ensure mixing, but do
this carefully so that no solution is lost. Finally, measure the absorption spectrum of
the I2 /KI solution (prepared in Sec. 1c) for this I2 concentration.
Then repeat all the absorption measurements for the other I2 concentration.
Laboratory report
1. Because the 353 nm absorbance is proportional to I
3 concentration (according to Beers
Law), the values of y (Eq. 7) can be directly computed from the ratios of 353 nm
absorbances measured for the aliquot additions to the 353 nm absorbance of the solution
in which all I2 is converted to I
3 . Evaluate y for the aliquot additions for the two two
different I2 concentrations.
2. The values of z (Eq. 8) can be computed from initial concentrations of I2 (a) and KI (b).
3. Plot all the data for both initial I2 concentrations on one graph with the y-axis being
the left side of Eq. 11 and the x-axis being z y. Fit the data to obtain the equilibrium
constant.
4. Report the standard change in Gibbs energy for the reaction at the temperature of your
experiment.
5. In your discussion, explain the important assumptions made in your data analysis.

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