Using Beers Law To Find An Equilibrium Constant For Iron(III) Thiocyanato Ion

Introduction

For the reaction
aA +bB cC +dD


it has been shown in class that
K
eq
=[C]
c
[D]
d

[A]
a
[B]
b


where Keq is the equilibrium constant for the reaction. The value of the equilibrium constant may be
calculated from experimental data if the concentrations of both the reactants and products at equilibrium
are known. Additionally, all equilibrium concentrations can be calculated if a single equilibrium
concentration is known along with all other initial concentrations are known. The student will use
spectrophotometry and Beers Law to determine this single equilibrium concentration.

The equilibrium reaction studied in this experiment is formation of the iron(III) thiocyanato
complex [Fe(SCN)
+2
] from the iron and thiocyanate ions:
Fe
+3
+ SCN
-
Fe(SCN)
+2


with the corresponding equilibrium expression:
K
eq
=[Fe(SCN)
+2
]

[Fe
+3
][SCN
-
]


The thiocyanate ion is colorless, the iron cation is slightly yellowish, but the iron(III) thiocyanato
complex is a deep red-orange.
Remember that many colored species will follow Beer's law:

A =abc

where A is the absorbance measured by a spectrophotometer, a is the absorptivity at a given wavelength
of light, b is the path length and c is the concentration of the absorbing species. Since the wavelength
and path length will be held constant, the relationship between absorbance and concentration should be
linear.

In order to use this method, we have a major problem that must be overcome. In order to make a
Beers Law plot, we need to know the concentration of [Fe(SCN)
2+
]. But, how can this be known, since
it is not known how much of the iron(III) ions will remain after mixing in the thiocyanate ion. At first it
may seem like we need the equilibrium constant to calculate how much [Fe(SCN)
+2
] will form and we
are in an impossible circular situation. So how do we escape? We stack the deck! Recall Le
Chateliers principle. First, establish the equilibrium by mixing iron(III) nitrate solution with potassium
thiocyanate. (What are the spectator ions????) Now lets add a truckload of thiocyanate ions to the
beaker. What happens according to Le Chateliers principle? The equilibrium shifts toward the right
and forms [Fe(SCN)
+2
]. By adding a large amount of thiocyanate ion, the iron(III) can be made to
completely react and exist as [Fe(SCN)
+2
]. By knowing how much iron(III) ions we started with, and
that we have converted these completely to [Fe(SCN)
+2
], allows us to know the concentration of the
[Fe(SCN)
+2
]. A Beers law plot constructed from solutions with a large amount of potassium
thiocyanate gives us the key to overcoming our circular problem.

From another set of solutions in which the equilibrium has not been pushed so far to the right,
we can now find Keq. The absorbance of these solutions is measured. From the Beers Law plot, the
equilibrium concentration of the [Fe(SCN)
+2
] is calculated. To mathematically solve for the value of
Keq, it is necessary to have values for all the concentration species: [Fe(SCN)
2+
], [Fe
3+
], and [SCN
-
] at
equilibrium. For this, a method called the 'ICE' approach will be used: Initial concentration, Change that
occurs, and the new Equilibrium concentration. Let's consider the experimental design. A standard
solution of SCN
-
are obtained and small amounts of a standard Fe(III) are added. The system reaches
equilibrium and absorbance values are obtained. The [Fe
3+
] and [SCN
-
] can be calculated using the
standard dilution expression. These, are initial concentrations since this is what was added before the
system came to equilibrium. The [Fe(SCN)
+2
], however, is an equilibrium concentration because it is
calculated from the absorbance of the equilibrium state. To use ICE, a table is set up under the
equilibrium expression. This topic is covered in detail in the textbook and in lecture. In this example,
the table is:
Fe(H
2
O)
3+
(aq) + SCN
-
(aq) Fe(SCN)
2+
(aq) + H
2
O (l)
Initial A B 0
Change -x -x +x
Equilibrium A-x B-x x


Substituting these values into equation 1 yields:
K
eq
= [Fe(SCN)
2+
] = X
[Fe
3+
][SCN
-
] (A-x)(B-x)
(1)

A value of Keq is found for each addition of iron(III) to the flask. 'A' and 'B' are found from the stock
concentrations and the dilution expression and 'x' is found from the Beers law plot. This method has an
advantage in that the precision of the Keq can be found by calculating the mean and standard deviation
of all the separate Keq values for each solution.

Procedure

PART I: A Beer's law plot for Fe[SCN]
2+

To prepare diluted iron(III) solutions for the Beers Law plot, obtain 35-40 mL of stock Fe(NO
3
)
3

solution that is 0.00250 M and has been made up using 0.5 M HNO3 as the solvent. Condition a 10 mL
volumetric pipet with a couple of milliliters of the solution. Repeat the conditioning with a second and
third volume. Fill the pipet to the mark and above being careful not to overfill and pull solution into the
rubber bulb. Using your forefinger, seal the pipet and allow small amounts of air into the pipet by
rocking your fingertip. This lowers the meniscus to the mark (if it goes below - refill!). Transfer the
pipet tip into a 100 mL volumetric flask and allow the solution to flow into the flask. Once the transfer
is completed, touch the tip of the pipet against the flask wall and give a quarter turn. The solution left in
the pipet should remain there! Do not blow it out. Add 0.5 M nitric acid to the flask while periodically
mixing. Fill the flask up to the base of the neck - invert and mix well. Continue filling until the meniscus
is on the line. Cap, invert and shake well, then revert. Repeat the latter step a total of 15 (fifteen) times.
Label this flask as diluted Fe
3+
. Calculate the final iron concentration in your notebook, and record.
Obtain about 35 mL of concentrated potassium thiocyanate that is 1.00 M.
Using your diluted Fe
3+
, the 1.00 M KSCN and 0.5 M HNO3, prepare 5 solutions with pipets
according to the table below in clean test tubes.
Table 1: Solutions to prepare a Beers Law plot for thiocyanatoiron(III) ion
Soln. No.
Diluted
Fe(NO
3
)
3
, mL
Concentrated
KSCN, mL
0.5 M HNO
3
,
mL
1 1 5 4
2 2 5 3
3 3 5 2
4 4 5 1
5 5 5 0

Measure the absorbance of each solution in the spectrophotometer using a distilled water blank at a
wavelength of 447 nm. Make a graph of absorbance vs. concentration. Perform linear regression (best
straight line, or in Excel terms, the trend line) and draw the best straight line through the data. Make
sure you have Excel put the equation of the line on the graph.

PART II: Determining the Equilibrium Constant
In this section we will need to use concentrated iron(III) ion and diluted thiocyanate ion. Be
careful to use the appropriate solutions! If the diluted KSCN is not available in lab, you might need to
make it as well!
Make five trial solutions for the Fe[SCN]
2+
equilibrium. Pipet 5 mL of 0.00250 M Fe(NO
3
)
3
into five
clean medium-sized test tubes. Pipet 1 mL, 2 mL, 3 mL, 4 mL, and 5 mL of 0.00250 M KSCN,
respectively into test tubes 1 - 5. Pipet 4 mL, 3 mL, 2 mL, 1 mL and 0 mL 0.5 M HNO3, respectively,
into each test tube so that all solutions have a total volume of 10.0 mL. Measure the absorbance at the
wavelength used in Part I and determine the Fe[SCN]
2+
concentration of each solution from the Beer's
law plot drawn in Part I.
From the concentration of the complex, determine the concentrations of the iron and thiocyanate ions,
and from these three concentrations determine an equilibrium constant for each trial. Report the
average value of Keq for this reaction.